Pyridine derivatives compounds for controlling invertebrate pests

ABSTRACT

The present invention relates to methods and uses of compounds of formulae I or II and the salts and N-oxides thereof, 
                         
wherein
 
A is a substituted or unsubstituted 5-membered heterocyclic radical;
 
X 1  is S, O or NR 1a , wherein R 1a  is selected from H, C 1 -C 10 -alkyl and the like; X 2  is OR 2a , NR 2b R 2c , S(O) m R 2d ; X 2  is OR 2a , NR 2b R 2c , S(O) m R 2d , wherein m is 0, 1 or 2, R 2a  is C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl and the like, R 2b , R 2c  are H, C 1 -C 4 -alkyl, C 1 -C 4 -haloalkyl and the like; X 3  is a lone pair or oxygen; R 1 , R 2  and R 3  are, inter alia, hydrogen, and R 1  is H, C 1 -C 10 -alkyl and the like. The present invention further relates to a method for controlling invertebrate pests, to a method for protecting plant propagation material and/or the plants which grow therefrom, to plant propagation material, comprising at least one compound according to the present invention, to a method for treating or protecting an animal from infestation or infection by parasites and to an agricultural composition containing at least one compound according to the present invention.

This application is a National Stage application of InternationalApplication No. PCT/EP2010/060243 filed Jul. 15, 2010, which claims thebenefit of U.S. Provisional Application No. 61/228,205 filed Jul. 24,2009, the entire contents of which are hereby incorporated herein byreference.

The present invention relates to pyridine compounds which can be usedfor combating and/or controlling invertebrate pests, in particulararthropod pests. The invention also relates to a method for controllinginvertebrate pests by using these compounds. The present invention alsorelates to seed and to an agricultural and veterinary compositioncomprising said compounds.

BACKGROUND OF INVENTION

Invertebrate pests and in particular arthropods and nematodes destroygrowing and harvested crops and attack wooden dwelling and commercialstructures, thereby causing large economic loss to the food supply andto property. While a large number of pesticidal agents are known, due tothe ability of target pests to develop resistance to said agents, thereis an ongoing need for new agents for combating invertebrate pests suchas insects, arachnids and nematodes. It is therefore an object of thepresent invention to provide compounds having a good pesticidal activityand showing a broad activity spectrum against a large number ofdifferent invertebrate pests, especially against difficult to controlinsects, arachnids and nematodes.

JP 2001-348378 describes methylisoxazoles-4-carboxilic acid derivativesand their use as pest controlling agent for agriculture and horticultureis mentioned.

EP 0573883 describes isoxazoles derivatives and their veterinary andmedical use.

WO 2000/29398 describes isothiazoles-carboxylic acid derivatives andtheir use as biocide is mentioned.

JP 2001-159610 describes isoxazoles carboxylic acids derivatives andtheir use as plant disease controlling agent is mentioned.

CN 1927838 describes aromatic and heteroaromatic N-pyridinylcarboxamidesuseful as agrochemical bactericides and fungicides.

It is an object of the present invention to provide compounds that havea good pesticidal activity, in particular insecticidal activity, andshow a broad activity spectrum against a large number of differentinvertebrate pests, especially against difficult to control insects.

It has been found that these objectives can be achieved by compounds ofthe formulae I and II below and by their salts, in particular theiragriculturally or veterinarily acceptable salts.

In a first aspect the present invention relates the use controllinginvertebrate pests which method comprises treating the pests, their foodsupply, their habitat or their breeding ground or a plant, seed, soil,area, material or environment in which the pests are growing or maygrow, or the materials, plants, seeds, soils, surfaces or spaces to beprotected from pest attack or infestation with a pesticidally effectiveamount of a compound of the formulae I or II or a salt or N-oxidethereof:

-   -   wherein    -   A is an oxazole or thiazole or imidazole or isoxazole or        isothiazole radical of the formulae A1a, A1, A2a, A2, A3a, A3

-   -   # denotes the binding site to the remainder of formulae I or II;    -   X³ is a lone pair or oxygen;    -   Z is O or S if z=0 or    -   Z is N if z=1    -   R¹ is hydrogen, CN, C₁-C₁₀-alkyl, C₁-C₁₀-haloalkyl,        C₃-C₁₀-cycloalkyl, C₃-C₁₀-halocycloalkyl, C₂-C₁₀-alkenyl,        C₂-C₁₀-haloalkenyl, C₂-C₁₀-alkynyl, C₃-C₁₀-haloalkynyl, OR^(a),        C(Y)R^(b), C(Y)OR^(c), S(O)₂R^(d), NR^(e)R^(f), C(Y)NR^(g)R^(h),        S(O)_(m)NR^(e)R^(f), C(Y)NR^(i)NR^(e)R^(f), phenyl, hetaryl,        heterocyclyl, C₁-C₅-alkylen-OR^(a), C₁-C₅-alkylen-CN,        phenyl-C₁-C₅-alkyl, hetaryl-C₁-C₅-alkyl,        heterocyclyl-C₁-C₅-alkyl, C₃-C₁₀-cycloalkyl-C₁-C₅-alkyl,        C₁-C₅-alkylen-C(Y)R^(b), —C₁-C₅-alkylen-C(Y)OR^(c),        C₁-C₅-alkylen-NR^(e)R^(f), C₁-C₅-alkylen-C(Y)NR^(g)R^(h),        C₁-C₅-alkylen-S(O)₂R^(d), C₁-C₅-alkylen-S(O)_(m)NR^(e)R^(d),        C₁-C₅-alkylen-C(Y)NR^(i)NR^(e)R^(f) wherein the last sixteen        mentioned radicals may be unsubstituted or may carry 1, 2, 3, 4        or 5 identical or different substituents R^(x) or R^(y) and        wherein m is 0, 1 or 2;    -   R² is hydrogen, halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl,        C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio,        C₁-C₄-haloalkylthio, C₁-C₄-alkylsulfinyl,        C₁-C₄-haloalkylsulfinyl, C₁-C₄-alkylsulfonyl,        C₁-C₄-haloalkylsulfonyl, C₃-C₆-cycloalkyl, C₃-C₆-halocycloalkyl,        C₂-C₄-alkenyl, C₂-C₄-haloalkenyl, C₂-C₄-alkynyl or        C₁-C₄-alkoxy-C₁-C₄-alkyl;    -   R³ is hydrogen, halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl,        C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio,        C₁-C₄-haloalkylthio C₁-C₄-alkylsulfinyl,        C₁-C₄-haloalkylsulfinyl, C₁-C₄-alkylsulfonyl,        C₁-C₄-haloalkylsulfonyl, C₃-C₆-cycloalkyl, C₃-C₆-halocycloalkyl,        C₂-C₄-alkenyl, C₂-C₄-haloalkenyl, C₂-C₄-alkynyl or        C₁-C₄-alkoxy-C₁-C₄-alkyl;    -   R⁴¹, R^(41a), R⁴², R⁴³, R^(43a), R⁵¹, R^(51a), R⁵², R^(52a), R⁵³        and R^(53a) are independently selected from the group consisting        of hydrogen, halogen, CN, NO₂, C₁-C₁₀-alkyl, C₃-C₁₀-cycloalkyl,        C₅-C₁₀-cycloalkenyl, C₃-C₁₀-cycloalkylmethyl, C₂-C₁₀-alkenyl,        C₂-C₁₀-alkynyl, wherein the aliphatic or cyclic moieties in the        6 last mentioned radicals may be unsubstituted, may be partially        or fully halogenated or may carry 1, 2 or 3 identical or        different substituents R^(y), OR^(a), C(Y)R^(b), C(Y)OR^(c),        S(O)_(m)R^(d), NR^(e)R^(f), C(Y)NR^(g)R^(h), phenyl,        phenyl-C₁-C₄-alkyl, phenoxy-C₁-C₄-alkyl, 5-membered hetaryl and        heterocyclyl-C₁-C₄-alkyl wherein heterocyclyl and the aromatic        ring of the 5 last mentioned radicals may be unsubstituted or        may carry 1, 2, 3, 4 or 5 identical or different substituents        R^(x),        -   with the proviso that either R^(41a) or R^(51a) is H if Z is            O;    -   R^(42a) is selected from the group consisting of hydrogen,        halogen, NO₂, C₁-C₁₀-alkyl, C₃-C₁₀-cycloalkyl,        C₅-C₁₀-cycloalkenyl, C₃-C₁₀-cycloalkylmethyl, C₂-C₁₀-alkenyl,        C₂-C₁₀-alkynyl, wherein the aliphatic or cyclic moieties in the        6 last mentioned radicals may be unsubstituted, may be partially        or fully halogenated or may carry 1, 2 or 3 identical or        different substituents R^(y), OR^(a), C(Y)R^(b), C(Y)OR^(c),        S(O)_(m)R^(d), NR^(e)R^(f), C(Y)NR^(g)R^(h), phenyl,        phenyl-C₁-C₄-alkyl, phenoxy-C₁-C₄-alkyl, 5-membered hetaryl and        heterocyclyl-C₁-C₄-alkyl wherein heterocyclyl and the aromatic        ring of the 5 last mentioned radicals may be unsubstituted or        may carry 1, 2, 3, 4 or 5 identical or different substituents        R^(x);    -   R⁶¹, R⁶², R⁶³ are selected from the group consisting of        hydrogen, NO₂, C₁-C₁₀-alkyl, C₃-C₁₀-cycloalkyl,        C₅-C₁₀-cycloalkenyl, C₃-C₁₀-cycloalkylmethyl, C₂-C₁₀-alkenyl,        C₂-C₁₀-alkynyl, wherein the aliphatic or cyclic moieties in the        6 last mentioned radicals may be unsubstituted, may be partially        or fully halogenated or may carry 1, 2 or 3 identical or        different substituents R^(y), OR^(a), C(Y)R^(b), C(Y)OR^(c),        S(O)_(m)R^(d), NR^(e)R^(f), C(Y)NR^(g)R^(h),        S(O)_(m)NR^(e)R^(f), C(Y)NR^(i)NR^(e)R^(f), heterocyclyl,        heterocyclyl-C₁-C₅-alkyl, heteroaryl, heteroaryl-C₁-C₅-alkyl,        C₃-C₁₀-cycloalkyl, C₃-C₁₀-cycloalkyl-C₁-C₅-alkyl, cycloalkenyl,        C₅-C₁₀-cycloalkenyl-C₁-C₅-alkyl, phenyl, phenyl-C₁-C₅-alkyl,        C₁-C₅-alkylen-ORB, C₁-C₅-alkylen-CN, C₁-C₅-alkylen-C(Y)R^(b),        C₁-C₅-alkylen-C(Y)OR^(c), C₁-C₅-alkylen-NR^(e)R^(f),        C₁-C₅-alkylen-C(Y)NR^(g)R^(h), C₁-C₅-alkylen-S(O)_(m)R^(d),        C₁-C₅-alkylen-S(O)_(m)NR^(e)R^(f),        C₁-C₅-alkylen-C(Y)NR^(i)NR^(e)R^(f), wherein the last nineteen        mentioned radicals may be unsubstituted or may carry 1, 2, 3, 4        or 5 identical or different substituents R^(x) or R^(y) and        wherein m is 0, 1 or 2;    -   Y is O or S;    -   X¹ is S, O or NR^(1a), wherein R^(1a) is selected from hydrogen,        C₁-C₁₀-alkyl, C₁-C₄-haloalkyl, C₃-C₁₀-cycloalkyl,        C₃-C₁₀-cycloalkylmethyl, C₃-C₁₀-halocycloalkyl, C₂-C₁₀-alkenyl,        C₂-C₁₀-haloalkenyl, C₂-C₁₀-alkynyl, C₁-C₁₀-alkoxy-C₁-C₄-alkyl,        OR^(a), phenyl, hetaryl, heterocyclyl, phenyl-C₁-C₄-alkyl,        hetaryl-C₁-C₄-alkyl, heterocyclyl-C₁-C₄-alkyl wherein the ring        in the six last mentioned radicals may be unsubstituted or may        carry 1, 2, 3, 4 or substituents which, independently of each        other, are selected from halogen, cyano, nitro, C₁-C₄-alkyl,        C₁-C₄-haloalkyl, C₁-C₄-alkoxy and C₁-C₄-haloalkoxy;    -   X² is OR^(2a), NR^(2b)R^(2c), S(O)_(m)R^(2d), wherein m is 0, 1        or 2, wherein        -   R^(2a) is selected from C₁-C₄-alkyl, C₁-C₄-haloalkyl,            C₃-C₆-cycloalkyl, C₃-C₆-halocycloalkyl, C₂-C₄-alkenyl,            C₂-C₄-haloalkenyl, C₂-C₄-alkynyl, C₁-C₄-alkoxy-C₁-C₄-alkyl,            phenyl, hetaryl, heterocyclyl, phenyl-C₁-C₄-alkyl,            hetaryl-C₁-C₄-alkyl and heterocyclyl-C₁-C₄-alkyl, wherein            the ring in the six last mentioned radicals may be            unsubstituted or may carry 1, 2, 3, 4 or substituents which,            independently of each other, are selected from halogen,            cyano, nitro, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy and            C₁-C₄-haloalkoxy, and wherein        -   R^(2b), R^(2c) are independently of each other selected from            hydrogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₃-C₆-cycloalkyl,            C₃-C₆-halocycloalkyl, C₂-C₄-alkenyl, C₂-C₄-haloalkenyl,            C₂-C₄-alkynyl, C₁-C₄-alkoxy-C₁-C₄-alkyl,            C₁-C₄-alkylcarbonyl, C₁-C₄-haloalkylcarbonyl,            C₁-C₄-alkylsulfonyl, C₁-C₄-haloalkylsulfonyl, phenyl,            phenylcarbonyl, phenylsulfonyl, hetaryl, hetarylcarbonyl,            hetarylsulfonyl, heterocyclyl, heterocyclylcarbonyl,            heterocyclylsulfonyl, phenyl-C₁-C₄-alkyl,            hetaryl-C₁-C₄-alkyl and heterocyclyl-C₁-C₄-alkyl wherein the            ring in the twelve last mentioned radicals may be            unsubstituted or may carry 1, 2, 3, 4 or 5 substituents            which, independently of each other, are selected from            halogen, cyano, nitro, C₁-C₄-alkyl, C₁-C₄-haloalkyl,            C₁-C₄-alkoxy and C₁-C₄-haloalkoxy, or        -   R^(2b) and R^(2c) together with the nitrogen atom to which            they are bound form a 5- or 6-membered, saturated or            unsaturated heterocycle, which may carry a further            heteroatom being selected from O, S and N as a ring member            atom and wherein the heterocycle may be unsubstituted or may            carry 1, 2, 3, 4 or 5 substituents which, independently of            each other, are selected from halogen, cyano, nitro,            C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy and            C₁-C₄-haloalkoxy, and wherein    -   R^(2d) is selected from C₁-C₄-alkyl, C₃-C₆-cycloalkyl,        C₃-C₆-halocycloalkyl, C₂-C₄-alkenyl, C₂-C₄-haloalkenyl,        C₂-C₄-alkynyl, C₁-C₄-alkoxy-C₁-C₄-alkyl, phenyl, hetaryl,        heterocyclyl, phenyl-C₁-C₄-alkyl, hetaryl-C₁-C₄-alkyl and        heterocyclyl-C₁-C₄-alkyl, wherein the ring in the six last        mentioned radicals may be unsubstituted or may carry 1, 2, 3, 4        or 5 substituents which, independently of each other, are        selected from halogen, cyano, nitro, C₁-C₄-alkyl,        C₁-C₄-haloalkyl, C₁-C₄-alkoxy and C₁-C₄-haloalkoxy; R^(a),        R^(b), R^(c) are independently of each other selected from        hydrogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₃-C₆-cycloalkyl,        C₃-C₆-cycloalkylmethyl, C₃-C₆-halocycloalkyl, C₂-C₄-alkenyl,        C₂-C₄-haloalkenyl, C₂-C₄-alkynyl, C₁-C₄-alkoxy-C₁-C₄-alkyl,        phenyl, hetaryl, heterocyclyl, phenyl-C₁-C₄-alkyl,        hetaryl-C₁-C₄-alkyl and heterocyclyl-C₁-C₄-alkyl, wherein the        ring in the six last mentioned radicals may be unsubstituted or        may carry 1, 2, 3, 4 or substituents which, independently of        each other, are selected from halogen, cyano, nitro,        C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy and C₁-C₄-haloalkoxy;    -   R^(d) is selected from C₁-C₄-alkyl, C₁-C₄-haloalkyl,        C₃-C₆-cycloalkyl, C₃-C₆-cycloalkylmethyl, C₃-C₆-halocycloalkyl,        C₂-C₄-alkenyl, C₂-C₄-haloalkenyl, C₂-C₄-alkynyl,        C₁-C₄-alkoxy-C₁-C₄-alkyl, phenyl, hetaryl, heterocyclyl,        phenyl-C₁-C₄-alkyl, hetaryl-C₁-C₄-alkyl and        heterocyclyl-C₁-C₄-alkyl wherein the ring in the six last        mentioned radicals may be unsubstituted or may carry 1, 2, 3, 4        or 5 substituents which are independently of each other selected        from halogen, cyano, nitro, C₁-C₄-alkyl, C₁-C₄-haloalkyl,        C₁-C₄-alkoxy and C₁-C₄-haloalkoxy;    -   R^(e), R^(f) are independently of each other selected from        hydrogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₃-C₆-cycloalkyl,        C₃-C₆-cycloalkylmethyl, C₃-C₆-halocycloalkyl, C₂-C₄-alkenyl,        C₂-C₄-haloalkenyl, C₂-C₄-alkynyl, C₁-C₄-alkoxy-C₁-C₄-alkyl,        C₁-C₄-alkylcarbonyl, C₁-C₄-haloalkylcarbonyl,        C₁-C₄-alkylsulfonyl, C₁-C₄-haloalkylsulfonyl, phenyl,        phenylcarbonyl, phenylsulfonyl, hetaryl, hetarylcarbonyl,        hetarylsulfonyl, heterocyclyl, heterocyclylcarbonyl,        heterocyclylsulfonyl, phenyl-C₁-C₄-alkyl, hetaryl-C₁-C₄-alkyl        and heterocyclyl-C₁-C₄-alkyl wherein the ring in the twelve last        mentioned radicals may be unsubstituted or may carry 1, 2, 3, 4        or 5 substituents which, independently of each other, are        selected from halogen, cyano, nitro, C₁-C₄-alkyl,        C₁-C₄-haloalkyl, C₁-C₄-alkoxy and C₁-C₄-haloalkoxy; or    -   R^(e) and R^(f) together with the nitrogen atom to which they        are bound form a 5- or 6-membered, saturated or unsaturated        heterocycle, which may carry a further heteroatom being selected        from O, S and N as a ring member atom and wherein the        heterocycle may be unsubstituted or may carry 1, 2, 3, 4 or 5        substituents which are independently of each other selected from        halogen, cyano, nitro, C₁-C₄-alkyl, C₁-C₄-haloalkyl,        C₁-C₄-alkoxy and C₁-C₄-haloalkoxy;    -   R^(g), R^(h) are independently of each other selected from        hydrogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₃-C₆-cycloalkyl,        C₃-C₆-halocycloalkyl, C₂-C₄-alkenyl, C₂-C₄-haloalkenyl,        C₂-C₄-alkynyl, C₁-C₄-alkoxy-C₁-C₄-alkyl, phenyl, hetaryl,        heterocyclyl, phenyl-C₁-C₄-alkyl, hetaryl-C₁-C₄-alkyl and        heterocyclyl-C₁-C₄-alkyl wherein the ring in the six last        mentioned radicals may be unsubstituted or may carry 1, 2, 3, 4        or substituents which are independently of each other selected        from halogen, cyano, nitro, C₁-C₄-alkyl, C₁-C₄-alkoxy and        C₁-C₄-haloalkoxy;    -   R^(i) is selected from hydrogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl,        C₃-C₆-cycloalkyl, C₃-C₆-cycloalkylmethyl, C₃-C₆-halocycloalkyl,        C₂-C₄-alkenyl, C₂-C₄-haloalkenyl, C₂-C₄-alkynyl,        C₁-C₄-alkoxy-C₁-C₄-alkyl, phenyl and phenyl-C₁-C₄-alkyl wherein        the phenyl ring in the two last mentioned radicals may be        unsubstituted or may carry 1, 2, 3, 4 or 5 substituents which        are independently of each other selected from halogen, cyano,        nitro, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy and        C₁-C₄-haloalkoxy;    -   R^(x) are independently of each other selected from cyano,        nitro, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylthio,        C₁-C₄-haloalkylthio, C₁-C₄-alkylsulfinyl, C₁-C₄-alkylsulfonyl,        C₁-C₄-haloalkylsulfonyl, C₁-C₁₀-alkylcarbonyl, C₃-C₆-cycloalkyl,        5- to 7-membered heterocyclyl, phenyl, C₃-C₆-cycloalkoxy, 3- to        6-membered heterocyclyloxy and phenoxy, wherein the last 6        mentioned radicals may be unsubstituted or may carry 1, 2, 3, 4        or 5 radicals R^(y); and wherein    -   R^(y) is selected from halogen, cyano, nitro, C₁-C₄-alkyl,        C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, S(O)_(m)R^(d),        S(O)_(m)NR^(e)R^(f), C₁-C₄-alkylcarbonyl,        C₁-C₄-haloalkylcarbonyl, C₁-C₄-alkoxycarbonyl,        C₁-C₄-haloalkoxycarbonyl, C₃-C₆-cycloalkyl,        C₃-C₆-halocycloalkyl, C₂-C₄-alkenyl, C₂-C₄-haloalkenyl,        C₂-C₄-alkynyl and C₁-C₄-alkoxy-C₁-C₄-alkyl wherein m is 0, 1 or        2 and R^(d) as above defined.

In a second aspect, the present invention provides a method forcontrolling invertebrate pests which method comprises treating thepests, their food supply, their habitat or their breeding ground or aplant, plant propagation material (such as seed), soil, area, materialor environment in which the pests are growing or may grow, or thematerials, plants, plant propagation materials (such as seeds), soils,surfaces or spaces to be protected from pest attack or infestation witha pesticidally effective amount of a compound of the formulae I or II ora salt or N-oxide thereof or with a pesticidally effective amount of anagricultural composition containing at least one compound of theformulae I or II or a salt or N-oxide thereof.

In a third aspect, the present invention provides a method forprotecting seed and/or the plants which grow therefrom, againstinfestation by invertebrate pests, which method comprises treating theseed with a pesticidally effective amount of a compound of the formulaeI or II or an agriculturally acceptable salt or N-oxide thereof. Afurther object of the present invention is seed, comprising at least onecompound of formulae I or II and/or an agriculturally acceptable salt orN-oxide thereof.

The invention further provides a method for treating or protecting ananimal from infestation or infection by parasites, especiallyectoparasites, which method comprises bringing the animal in contactwith a parasiticidally effective amount of a compound of the formulae Ior II or a veterinally acceptable salt or N-oxide thereof as definedabove. Bringing the animal in contact with the compound I or II, itssalt or the veterinary composition of the invention means applying oradministering it to the animal.

Therefore, the compounds of the formulae I and II and their salts, inparticular their agriculturally or veterinarily acceptable salts, andtheir N-oxides are also part of the invention.

Another object of the present invention is an agricultural compositioncontaining at least one compound of the formulae I or II as definedabove and/or an agriculturally acceptable salt or an N-oxide thereof andat least one liquid or solid carrier.

Another object of the present invention is a veterinary compositioncontaining at least one compound of the formulae I or II as definedabove and/or a veterinarily acceptable salt or an N-oxide thereof and atleast one veterinarily acceptable liquid or solid carrier.

The present invention further relates to plant propagation material,such as seed, comprising at least one compound of formulae I or II asdefined herein.

The present invention further relates to the uses of compounds offormulae I or II as defined herein for controlling invertebrate pests.

In the compounds of formulae I or II the substituents on A or thepyridyl ring may contain one or more centers of chirality. In this casethe compounds of the formulae I or II can be present in the form ofdifferent enantiomers or diastereomers, depending on the substituents.In case of the formula II, the compound II may also exist as a cis- ortrans-isomer with respect to the N═C axis. The present invention relatesto every possible stereoisomer of the compounds of general formulae I orII, i.e. to single enantiomers or diastereomers, as well as to mixturesthereof.

The compounds of formulae I or II may be amorphous or may exist in oneor more different crystalline states (polymorphs) which may have adifferent macroscopic properties such as stability or show differentbiological properties such as activities.

The present invention includes both amorphous and crystalline compoundsof formulae I or II, mixtures of different crystalline states of therespective compound I or II, as well as amorphous or crystalline saltsthereof.

Salts of the compounds of the formulae I or II are preferablyagriculturally and veterinarily acceptable salts. They can be formed ina customary method, e.g. by reacting the compound with an acid of theanion in question if the compound of formula I has a basic functionalityor by reacting an acidic compound of formulae I or II with a suitablebase.

Agriculturally useful salts of the compounds I and II encompassespecially the salts of those cations or the acid addition salts ofthose acids whose cations and anions, respectively, have no adverseeffect on the pesticidal action of the compounds I or II. Suitablecations are thus in particular the ions of the alkali metals, preferablysodium and potassium, of the alkaline earth metals, preferably calcium,magnesium and barium, of the transition metals, preferably manganese,copper, zinc and iron, and also the ammonium ion which, if desired, maycarry one to four C₁-C₄-alkyl substituents and/or one phenyl or benzylsubstituent, preferably diisopropylammonium, tetramethylammonium,tetrabutylammonium, trimethylbenzylammonium, furthermore phosphoniumions, sulfonium ions, preferably tri(C₁-C₄-alkyl)sulfonium, andsulfoxonium ions, preferably tri(C₁-C₄-alkyl)sulfoxonium.

Anions of useful acid addition salts are primarily chloride, bromide,fluoride, hydrogen-sulfate, sulfate, dihydrogenphosphate,hydrogenphosphate, phosphate, nitrate, bicarbonate, carbonate,hexafluorosilicate, hexafluorophosphate, benzoate, and the anions ofC₁-C₄-alkanoic acids, preferably formate, acetate, propionate andbutyrate. They can be formed by reacting compounds of formulae (I) and(II) with an acid of the corresponding anion, preferably of hydrochloricacid, hydrobromic acid, sulfuric acid, phosphoric acid or nitric acid.

Veterinarily acceptable salts of the compounds of formula (I) encompassespecially the salts of those cations or the acid addition salts whichare known and accepted in the art for the formation of salts forveterinary use. Suitable acid addition salts, e.g. formed by compoundsof formulae I or II containing a basic nitrogen atom, e.g. an aminogroup, include salts with inorganic acids, for example hydrochlorids,sulphates, phosphates, and nitrates and salts of organic acids forexample acetic acid, maleic acid, e.g. the monoacid salts or diacidsalts of maleic acid, dimaleic acid, fumaric acid, e.g. the monoacidsalts or diacid salts of fumaric acid, difumaric acid, methane sulfenicacid, methane sulfonic acid, and succinic acid.

The term “N-oxide” includes any compound of the formulae I or II which,apart from the pyridine nitrogen that carries the moiety X³, has atleast one tertiary nitrogen atom that is oxidized to an N-oxide moiety.

The term “invertebrate pest” as used herein encompasses animalpopulations, such as insects, arachnids and nematodes, which may attackplants thereby causing substantial damage to the plants attacked, aswell as ectoparasites which may infest animals, e.g. mammals, birds orfish, thereby causing damage to the animals infested.

The term “plant propagation material” as used herein includes all thegenerative parts of the plant such as seeds and vegetative plantmaterial such as cuttings and tubers (e.g. potatoes), which can be usedfor the multiplication of the plant. This includes seeds, roots, fruits,tubers, bulbs, rhizomes, shoots, sprouts and other parts of plants.Seedlings and young plants, which are to be transplanted aftergermination or after emergence from soil, may also be included. Theseplant propagation materials may be treated prophylactically with a plantprotection compound either at or before planting or transplanting.

The term “cultivated plants” as used herein includes plants which havebeen modified by breeding, mutagenesis or genetic engineering.Genetically modified plants are plants, which genetic material has beenso modified by the use of recombinant DNA techniques that under naturalcircumstances cannot readily be obtained by cross breeding, mutations ornatural recombination. Typically, one or more genes have been integratedinto the genetic material of a genetically modified plant in order toimprove certain properties of the plant. Such genetic modifications alsoinclude but are not limited to targeted post-transitional modificationof protein(s) (oligo- or polypeptides) poly for example by glycosylationor polymer additions such as prenylated, acetylated or farnesylatedmoieties or PEG moieties (e.g. as disclosed in Biotechnol Prog. 2001July-August; 17(4):720-8, Protein Eng Des Sel. 2004 January;17(1):57-66, Nat. Protoc. 2007; 2(5):1225-35, Curr. Opin. Chem. Biol.2006 October; 10(5):487-91. Epub 2006 Aug. 28, Biomaterials. 2001 March;22(5):405-17, Bioconjug Chem. 2005 January-February; 16(1):113-21).

The term “cultivated plants” as used herein further includes plants thathave been rendered tolerant to applications of specific classes ofherbicides, such as hydroxy-phenylpyruvate dioxygenase (HPPD)inhibitors; acetolactate synthase (ALS) inhibitors, such as sulfonylureas (see e.g. U.S. Pat. No. 6,222,100, WO 01/82685, WO 00/26390, WO97/41218, WO 98/02526, WO 98/02527, WO 04/106529, WO 05/20673, WO03/14357, WO 03/13225, WO 03/14356, WO 04/16073) or imidazolinones (seee.g. U.S. Pat. No. 6,222,100, WO 01/82685, WO 00/26390, WO 97/41218, WO98/02526, WO 98/02527, WO 04/106529, WO 05/20673, WO 03/14357, WO03/13225, WO 03/14356, WO 04/16073); enolpyruvylshikimate-3-phosphatesynthase (EPSPS) inhibitors, such as glyphosate (see e.g. WO 92/00377);glutamine synthetase (GS) inhibitors, such as glufosinate (see e.g.EP-A-0242236, EP-A-242246) or oxynil herbicides (see e.g. U.S. Pat. No.5,559,024) as a result of conventional methods of breeding or geneticengineering. Several cultivated plants have been rendered tolerant toherbicides by conventional methods of breeding (mutagenesis), forexample Clearfield® summer rape (Canola) being tolerant toimidazolinones, e.g. imazamox. Genetic engineering methods have beenused to render cultivated plants, such as soybean, cotton, corn, beetsand rape, tolerant to herbicides, such as glyphosate and glufosinate,some of which are commercially available under the trade namesRoundupReady® (glyphosate) and LibertyLink® (glufosinate).

The term “cultivated plants” as used herein further includes plants thatare by the use of recombinant DNA techniques capable to synthesize oneor more insecticidal proteins, especially those known from the bacterialgenus bacillus, particularly from bacillus thuringiensis, such asä-endotoxins, a g. CryIA(b), CryIA(c), CryIF, CryIF(a2), CryIIA(b),CryIIIA, CryIIIB(b1) or Cry9c; vegetative insecticidal proteins (VIP),e.g. VIP1, VIP2, VIP3 or VIP3A; insecticidal proteins of bacteriacolonizing nematodes, for example Photorhabdus spp. or Xenorhabdus spp.;toxins produced by animals, such as scorpion toxins, arachnid toxins,wasp toxins, or other insect-specific neurotoxins; toxins produced byfungi, such Streptomycetes toxins, plant lectins, such as pea or barleylectins; agglutinins; proteinase inhibitors, such as trypsin inhibitors,serine protease inhibitors, patatin, cystatin or papain inhibitors;ribosome-inactivating proteins (RIP), such as ricin, maize-RIP, abrin,luffin, saporin or bryodin; steroid metabolism enzymes, such as3-hydroxysteroid oxidase, ecdysteroid-IDP-glycosyl-transferase,cholesterol oxidases, ecdysone inhibitors or HMG-CoA-reductase; ionchannel blockers, such as blockers of sodium or calcium channels;juvenile hormone esterase; diuretic hormone receptors (helicokininreceptors); stilben synthase, bibenzyl synthase, chitinases orglucanases. In the context of the present invention these insecticidalproteins or toxins are to be understood expressly also as pre-toxins,hybrid proteins, truncated or otherwise modified proteins. Hybridproteins are characterized by a new combination of protein domains,(see, for example WO 02/015701). Further examples of such toxins orgenetically-modified plants capable of synthesizing such toxins aredisclosed, for example, in EP-A 374 753, WO 93/007278, WO 95/34656, EP-A427 529, EP-A 451 878, WO 03/018810 and WO 03/052073. The methods forproducing such genetically modified plants are generally known to theperson skilled in the art and are described, for example, in thepublications mentioned above. These insecticidal proteins contained inthe genetically modified plants impart to the plants producing theseproteins protection from harmful pests from certain taxonomic groups ofarthropods insects, particularly to beetles (Coleoptera), flies(Diptera), and butterflies and moths (Lepidoptera) and to plantparasitic nematodes (Nematoda).

The term “cultivated plants” as used herein further includes plants thatare by the use of recombinant DNA techniques capable to synthesize oneor more proteins to increase the resistance or tolerance of those plantsto bacterial, viral or fungal pathogens. Examples of such proteins arethe so-called “pathogenesis-related proteins” (PR proteins, see, forexample EP-A 0 392 225), plant disease resistance genes (for examplepotato cultivars, which express resistance genes acting againstPhytophthora infestans derived from the mexican wild potato Solanumbulbocastanum) or T4-lyso-zym (e.g. potato cultivars capable ofsynthesizing these proteins with increased resistance against bacteriasuch as Erwinia amylvora). The methods for producing such geneticallymodified plants are generally known to the person skilled in the art andare described, for example, in the publications mentioned above.

The term “cultivated plants” as used herein further includes plants thatare by the use of recombinant DNA techniques capable to synthesize oneor more proteins to increase the productivity (e.g. bio mass production,grain yield, starch content, oil content or protein content), toleranceto drought, salinity or other growth-limiting environ-mental factors ortolerance to pests and fungal, bacterial or viral pathogens of thoseplants.

The term “cultivated plants” as used herein further includes plants thatcontain by the use of recombinant DNA techniques a modified amount ofsubstances of content or new substances of content, specifically toimprove human or animal nutrition, for example oil crops that producehealth-promoting long-chain omega-3 fatty acids or unsaturated omega-9fatty acids (e.g. Nexera® rape).

The term “cultivated plants” as used herein further includes plants thatcontain by the use of recombinant DNA techniques a modified amount ofsubstances of content or new substances of content, specifically toimprove raw material production, for example potatoes that produceincreased amounts of amylopectin (e.g. Amflora® potato).

The organic moieties mentioned in the above definitions of the variablesare—like the term halogen—collective terms for individual listings ofthe individual group members. The prefix C_(n)-C_(m) indicates in eachcase the possible number of carbon atoms in the group.

The term halogen denotes in each case fluorine, bromine, chlorine oriodine, in particular fluorine, chlorine or bromine.

The term “alkyl” as used herein and in the alkyl moieties ofalkoxyalkyl, alkylamino, dialkylamino, alkylcarbonyl, alkylthio,alkylsulfinyl and alkylsulfonyl denotes in each case a straight-chain orbranched alkyl group having usually from 1 to 10 carbon atoms,frequently from 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms.Examples of an alkyl group are methyl, ethyl, n-propyl, iso-propyl,n-butyl, 2-butyl, iso-butyl, tert-butyl, n-pentyl, 1-methylbutyl,2-methylbutyl, 3-methylbutyl, 2,2-dimethylpropyl, 1-ethylpropyl,n-hexyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl,2-methylpentyl, 3-methylpentyl, 4-methylpentyl, 1,1-dimethylbutyl,1,2-dimethylbutyl, 1,3-dimethylbutyl, 2,2-dimethylbutyl,2,3-dimethylbutyl, 3,3-dimethylbutyl, 1-ethylbutyl, 2-ethylbutyl,1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl,1-ethyl-2-methylpropyl, n-heptyl, 1-methylhexyl, 2-methylhexyl,3-methylhexyl, 4-methylhexyl, 5-methylhexyl, 1-ethylpentyl,2-ethylpentyl, 3-ethylpentyl, 1-propylpentyl, n-oxtyl, 1-methyloctyl,2-methylheptyl, 1-ethylhexyl, 2-ethylhexyl, 1,2-dimethylhexyl,1-propylpentyl and 2-propylpentyl.

The term “haloalkyl” as used herein and in the haloalkyl moieties ofhaloalkylthio and haloalkylsulfonyl, denotes in each case astraight-chain or branched alkyl group having usually from 1 to 10carbon atoms, frequently from 1 to 6 carbon atoms, wherein the hydrogenatoms of this group are partially or totally replaced with halogenatoms. Preferred haloalkyl moieties are selected from C₁-C₄-haloalkyl,more preferably from C₁-C₂-haloalkyl, in particular fromC₁-C₂-fluoroalkyl such as fluoromethyl, difluoro-methyl,trifluoromethyl, 1-fluoroethyl, 2-fluoroethyl, 2,2-difluoroethyl,2,2,2-trifluoroethyl, pentafluoroethyl, heptafluoroisopropyl and thelike.

The term “alkoxy” as used herein denotes in each case a straight-chainor branched alkyl group which is bound via an oxygen atom and hasusually from 1 to 10 carbon atoms, frequently from 1 to 6 carbon atoms,preferably 1 to 4 carbon atoms. Examples of an alkoxy group are methoxy,ethoxy, n-propoxy, iso-propoxy, n-butyloxy, 2-butyloxy, iso-butyloxy,tert.-butyloxy, pentyloxy, 1-methylbutyloxy, 2-methylbutyloxy,3-methylbutyloxy, 2,2-dimethylpropyloxy, 1-ethylpropyloxy, hexyloxy,1,1-dimethylpropyloxy, 1,2-dimethylpropyloxy, 1-methylpentyloxy,2-methylpentyloxy, 3-methylpentyloxy, 4-methylpentyloxy,1,1-dimethylbutyloxy, 1,2-dimethylbutyloxy, 1,3-dimethylbutyloxy,2,2-dimethylbutyloxy, 2,3-dimethylbutyloxy, 3,3-dimethylbutyloxy,1-ethylbutyloxy, 2-ethylbutyloxy, 1,1,2-trimethylpropyloxy,1,2,2-trimethylpropyloxy, 1-ethyl-1-methylpropyloxy,1-ethyl-2-methylpropyloxy n-heptyloxy, 1-methylhexyloxy,2-methylhexyloxy, 3-methylhexyloxy, 4-methylhexyloxy, 5-methylhexyloxy,1-ethylpentyloxy, 2-ethylpentyloxy, 3-ethylpentyloxy, 1-propylpentyloxy,n-oxtyloxy, 1-methyloctyloxy, 2-methylheptyloxy, 1-ethylhexyloxy,2-ethylhexyloxy, 1,2-dimethylhexyloxy, 1-propylpentoxy and2-propylpentyloxy.

The term “haloalkoxy” as used herein denotes in each case astraight-chain or branched alkoxy group having from 1 to 10 carbonatoms, frequently from 1 to 6 carbon atoms, preferably 1 to 4 carbonatoms, wherein the hydrogen atoms of this group are partially or totallyreplaced with halogen atoms, in particular fluorine atoms. Preferredhaloalkoxy moieties include C₁-C₄-haloalkoxy, in particularC₁-C₂-fluoroalkoxy, such as fluoromethoxy, difluoromethoxy,trifluoromethoxy, 1-fluoroethoxy, 2-fluoroethoxy, 2,2-difluoroethoxy,2,2,2-trifluoroethoxy, 2-chloro-2-fluoroethoxy,2-chloro-2,2-difluoro-ethoxy, 2,2-dichloro-2-fluorethoxy,2,2,2-trichloroethoxy, pentafluoroethoxy and the like.

The term “cycloalkyl” as used herein and in the cycloalkyl moieties ofC₃-C₁₀-cycloalkylmethyl denotes in each case a mono- or bicycliccycloaliphatic radical having usually from 3 to 10 C atoms or 3 to 6 Catoms, such as cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,cycloheptyl, cyclooctyl, bicyclo[2.1.1]hexyl, bicyclo[3.1.1]heptyl,bicyclo[2.2.1]heptyl, and bicyclo[2.2.2]octyl.

The term “halocycloalkyl” as used herein and in the halocycloalkylmoieties of C₃-C₁₀-halocycloalkyl-methyl denotes in each case a mono- orbicyclic cycloaliphatic radical having usually from 3 to 10 C atoms or 3to 6 C atoms, wherein at least one, e.g. 1, 2, 3, 4 or 5 of the hydrogenatoms are replaced by halogen, in particular by fluorine or chlorine.Examples are 1- and 2-fluorocyclopropyl, 1,2-, 2,2- and2,3-difluorocyclopropyl, 1,2,2-trifluorocyclopropyl,2,2,3,3-tetrafluorocyclpropyl, 1- and 2-chlorocyclopropyl, 1,2-, 2,2-and 2,3-dichlorocyclopropyl, 1,2,2-trichlorocyclopropyl,2,2,3,3-tetrachlorocyclpropyl, 1-,2- and 3-fluorocyclopentyl, 1,2-,2,2-, 2,3-, 3,3-, 3,4-, 2,5-difluorocyclopentyl, 1-,2- and3-chlorocyclopentyl, 1,2-, 2,2-, 2,3-, 3,3-, 3,4-,2,5-dichlorocyclopentyl and the like.

The term “alkenyl” as used herein denotes in each case a singlyunsaturated hydrocarbon radical having usually 2 to 10, e.g. 2, 3, 4, 5,6, 7 or 8 C-atoms, e.g. vinyl, allyl (2-propen-1-yl), 1-propen-1-yl,2-propen-2-yl, methallyl (2-methylprop-2-en-1-yl), 2-buten-1-yl,3-buten-1-yl, 2-penten-1-yl, 3-penten-1-yl, 4-penten-1-yl,1-methylbut-2-en-1-yl, 2-ethylprop-2-en-1-yl and the like.

The term “alkynyl” as used herein denotes in each case a singlyunsaturated hydrocarbon radical having usually 2 to 10, e.g. 2, 3, 4, 5,6, 7 or 8 C-atoms, e.g. ethynyl, propargyl (2-propyn-1-yl),1-propyn-1-yl, 1-methylprop-2-yn-1-yl), 2-butyn-1-yl, 3-butyn-1-yl,1-pentyn-1-yl, 3-pentyn-1-yl, 4-pentyn-1-yl, 1-methylbut-2-yn-1-yl,1-ethylprop-2-yn-1-yl and the like.

The term “C₁-C₄-alkoxy-C₁-C₄-alkyl” as used herein refers to C₁-C₄-alkylwherein 1 carbon atom carries a C₁-C₄-alkoxy radical as mentioned above.Examples are CH₂OCH₃, CH₂—OC₂H₅, n-propoxymethyl, CH₂—OCH(CH₃)₂,n-butoxymethyl, (1-methylpropoxy)-methyl, (2-methylpropoxy)methyl,CH₂—OC(CH₃)₃, 2-(methoxy)ethyl, 2-(ethoxy)ethyl, 2-(n-propoxy)-ethyl,2-(1-methylethoxy)-ethyl, 2-(n-butoxy)ethyl, 2-(1-methylpropoxy)-ethyl,2-(2-methylpropoxy)-ethyl, 2-(1,1-dimethylethoxy)-ethyl,2-(methoxy)-propyl, 2-(ethoxy)-propyl, 2-(n-propoxy)-propyl,2-(1-methylethoxy)-propyl, 2-(n-butoxy)-propyl,2-(1-methylpropoxy)-propyl, 2-(2-methylpropoxy)-propyl,2-(1,1-dimethylethoxy)-propyl, 3-(methoxy)-propyl, 3-(ethoxy)-propyl,3-(n-propoxy)-propyl, 3-(1-methylethoxy)-propyl, 3-(n-butoxy)-propyl,3-(1-methylpropoxy)-propyl, 3-(2-methylpropoxy)-propyl,3-(1,1-dimethylethoxy)-propyl, 2-(methoxy)-butyl, 2-(ethoxy)-butyl,2-(n-propoxy)-butyl, 2-(1-methylethoxy)-butyl, 2-(n-butoxy)-butyl,2-(1-methylpropoxy)-butyl, 2-(2-methylpropoxy)-butyl,2-(1,1-dimethylethoxy)-butyl, 3-(methoxy)-butyl, 3-(ethoxy)-butyl,3-(n-propoxy)-butyl, 3-(1-methylethoxy)-butyl, 3-(n-butoxy)-butyl,3-(1-methylpropoxy)-butyl, 3-(2-methylpropoxy)-butyl,3-(1,1-dimethylethoxy)-butyl, 4-(methoxy)-butyl, 4-(ethoxy)-butyl,4-(n-propoxy)-butyl, 4-(1-methylethoxy)-butyl, 4-(n-butoxy)-butyl,4-(1-methylpropoxy)-butyl, 4-(2-methylpropoxy)-butyl,4-(1,1-dimethylethoxy)-butyl and the like.

The term “alkylthio “(alkylsulfanyl: alkyl-S—)” as used herein refers toa straight-chain or branched saturated alkyl group having 1 to 10 carbonatoms, preferably 1 to 4 carbon atoms (═C₁-C₄-alkylthio) (as mentionedabove) which is attached via a sulfur atom.

The term “haloalkylthio” as used herein refers to a alkylthio group asmentioned above wherein the hydrogen atoms are partially or fullysubstituted by fluorine, chlorine, bromine and/or iodine.

The term “alkylsulfinyl” (alkylsulfoxyl: C₁-C₆-alkyl-S(═O)—), as usedherein refers to a straight-chain or branched saturated alkyl group (asmentioned above) having 1 to 10 carbon atoms, preferably 1 to 4 carbonatoms (═C₁-C₄-alkylsulfinyl) bonded through the sulfur atom of thesulfinyl group at any position in the alkyl group.

The term “haloalkylsulfinyl” as used herein refers to a alkylsulfinylgroup as mentioned above wherein the hydrogen atoms are partially orfully substituted by fluorine, chlorine, bromine and/or iodine.

The term “alkylsulfonyl” (alkyl-S(═O)₂—) as used herein refers to astraight-chain or branched saturated alkyl group having 1 to 10 carbonatoms, preferably 1 to 4 carbon atoms (═C₁-C₄-alkylsulfonyl) (asmentioned above) which is bonded via the sulfur atom of the sulfonylgroup at any position in the alkyl group.

The term “haloalkylsulfonyl” as used herein refers to a alkylsulfonylgroup as mentioned above wherein the hydrogen atoms are partially orfully substituted by fluorine, chlorine, bromine and/or iodine.

The term “heterocyclyl” includes in general 5-, 6-, 7- or 8-memberedmonoheterocyclic radicals and 8 to 10 membered bicyclic heterocyclicradicals, the mono- and bicyclic radicals may be saturated, unsaturatedor aromatic (=hetaryl). The mono- and bicyclic heterocyclic radicals asusually comprise 1, 2, 3 or 4 heteroatoms selected from N, O and S asring members.

The term “hetaryl” includes monocyclic 5- or 6-membered heteroaromaticradicals comprising as ring members 1, 2, 3 or 4 heteroatoms selectedfrom N, O and S. Examples of 5- or 6-membered heteroaromatic radicalsinclude pyridyl, i.e. 2-, 3-, or 4-pyridyl, pyrimidinyl, i.e. 2-, 4- or5-pyrimidinyl, pyrazinyl, pyridazinyl, i.e. 3- or 4-pyridazinyl,thienyl, i.e. 2- or 3-thienyl, furyl, i.e. 2- or 3-furyl, pyrrolyl, i.e.2- or 3-pyrrolyl, oxazolyl, i.e. 2-, 3- or 5-oxazolyl, isoxazolyl, i.e.3-, 4- or 5-isoxazolyl, thiazolyl, i.e. 2-, 3- or 5-thiazolyl,isothiazolyl, i.e. 3-, 4- or 5-isothiazolyl, pyrazolyl, i.e. 1-, 3-, 4-or 5-pyrazolyl, i.e. 1-, 2-, 4- or 5-imidazolyl, oxadiazolyl, e.g. 2- or5-[1,3,4]oxadiazolyl, 4- or 5-(1,2,3-oxadiazol)yl, 3- or5-(1,2,4-oxadiazol)yl, 2- or 5-(1,3,4-thiadiazol)yl, thiadiazolyl, e.g.2- or 5-(1,3,4-thiadiazol)yl, 4- or 5-(1,2,3-thiadiazol)yl, 3- or5-(1,2,4-thiadiazol)yl, triazolyl, e.g. 1H-, 2H- or3H-1,2,3-triazol-4-yl, 2H-triazol-3-yl, 1H-, 2H-, or 4H-1,2,4-triazolyland tetrazolyl, i.e. 1H- or 2H-tetrazolyl.

The term “hetaryl” also includes bicyclic 8 to 10-memberedheteroaromatic radicals comprising as ring members 1, 2 or 3 heteroatomsselected from N, O and S, wherein a 5- or 6-membered heteroaromatic ringis fused to a phenyl ring or to a 5- or 6-membered heteroaromaticradical. Examples of a 5- or 6-membered heteroaromatic ring fused to aphenyl ring or to a 5- or 6-membered heteroaromatic radical includebenzofuranyl, benzothienyl, indolyl, indazolyl, benzimidazolyl,benzoxathiazolyl, benzoxadiazolyl, benzothiadiazolyl, benzoxazinyl,chinolinyl, isochinolinyl, purinyl, 1,8-naphthyridyl, pteridyl,pyrido[3,2-d]pyrimidyl or pyridoimidazolyl and the like. These fusedhetaryl radicals may be bonded to the remainder of the molecule via anyring atom of 5- or 6-membered heteroaromatic ring or via a carbon atomof the fused phenyl moiety.

Examples of saturated or unsaturated membered heterocyclic ringscomprise saturated or unsaturated, non-aromatic heterocyclic rings, suchas pyrrolidinyl, pyrazolinyl, imidazolinyl, pyrrolinyl, pyrazolinyl,imidazolinyl, tetrahydrofuranyl, dihydrofuranyl, 1,3-dioxolanyl,dioxolenyl, thiolanyl, dihydrothienyl, oxazolidinyl, isoxazolidinyl,oxazolinyl, isoxazolinyl, thiazolinyl, isothiazolinyl, thiazolidinyl,isothiazolidinyl, oxathiolanyl, piperidinyl, piperazinyl, pyranyl,dihydropyranyl, tetrahydropyranyl, 1,3- and 1,4-dioxanyl, thiopyranyl,dihydrothiopyranyl, tetrahydrothiopyranyl, morpholinyl, thiazinyl andthe like. Examples for heterocyclic ring also comprising 1 or 2 carbonylgroups as ring members comprise pyrrolidin-2-only,pyrrolidin-2,5-dionyl, imidazolidin-2-only, oxazolidin-2-only,thiazolidin-2-only and the like.

The terms “phenyl-C₁-C₄-alkyl” and “phenoxy-C₁-C₄-alkyl” refers tophenyl or phenoxy, respectively, which are bound via a C₁-C₄-alkylgroup, in particular a methyl group (=hetarylmethyl), to the remainderof the molecule, examples including benzyl, 1-phenylethyl,2-phenylethyl, 2-phenoxyethyl etc.

The terms “heterocyclyl-C₁-C₄-alkyl” and “hetaryl-C₁-C₄-alkyl” refers toheterocyclyl or hetaryl, respectively, as defined above which are boundvia a C₁-C₄-alkyl group, in particular a methyl group(=heterocyclylmethyl or hetarylmethyl, respectively), to the remainderof the molecule.

The remarks made below as to preferred embodiments of the variables ofthe compounds of the formulae I or II, of the features of the use andmethod according to the invention and of the composition of theinvention are valid on their own as well as—preferably—in combinationwith each other.

A preferred embodiment of the invention relates to the method and usesof pyridine compounds of the formula I, to their salts, to theirN-oxides. Amongst the compounds of the formula I, preference is given tothose compounds, wherein X¹ in formula I is oxygen, sulphur or a moietyN—R^(1a).

Particular preference is given to the methods and uses of thosecompounds of the formula I wherein X¹ is oxygen.

In the methods and uses of compounds of the formula I, wherein X¹ isNR^(1a), a particular embodiment relates to the uses of those compounds,wherein R^(1a) is C₁-C₆-alkyl, C₁-C₆-haloalkyl, C₃-C₆-cycloalkyl,C₃-C₆-cycloalkylmethyl, C₃-C₆-halocycloalkyl, C₂-C₆-alkenyl,C₂-C₆-haloalkenyl, C₂-C₆-alkynyl, C₁-C₄-alkoxy-C₁-C₆-alkyl, phenyl,hetaryl, phenyl-C₁-C₄-alkyl and hetaryl-C₁-C₄-alkyl, wherein thearomatic ring in the four last mentioned radicals may be unsubstitutedor may carry 1, 2, 3, 4 or substituents which, independently of eachother, are selected from the group consisting of halogen, cyano, nitro,C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy and C₁-C₄-haloalkoxy, or amoiety ORB. In particular, R^(1a) is C₁-C₆-alkyl,C₃-C₆-cycloalkylmethyl, C₃-C₆-alkenyl, C₃-C₆-alkynyl,C₁-C₄-alkoxy-C₁-C₄-alkyl or a moiety ORB, wherein R^(a) is as definedabove and in particular selected from C₁-C₆-alkyl,C₃-C₆-cycloalkylmethyl, C₃-C₆-alkenyl, C₃-C₆-alkynyl andC₁-C₄-alkoxy-C₁-C₄-alkyl.

Amongst the methods and uses of compounds of the formula I, preferenceis given to the uses of those compounds, wherein R¹ is hydrogen, CN,C₁-C₁₀-alkyl, C₂-C₁₀-alkenyl, C₂-C₁₀-haloalkenyl, C₂-C₁₀-alkynyl,C₁-C₄-alkoxy-C₁-C₁₀-alkyl, C₁-C₄-alkylene-CN, OR^(a), C(Y)R^(b), C(Y)ORGor S(O)₂R^(d). More preference is given to the use of compounds offormula I, wherein R¹ is hydrogen, C₁-C₁₀-alkyl, C₁-C₁₀-haloalkyl,C₂-C₁₀-alkenyl, C₂-C₁₀-haloalkenyl, C₂-C₁₀-alkynyl,C₁-C₄-alkoxy-C₁-C₁₀-alkyl or C₁-C₄-alkylene-CN, in particular hydrogen,C₁-C₃-alkyl or C₁-C₄-alkylene-CN, in particular hydrogen, methyl orethyl.

Another embodiment of the invention relates to the methods and uses ofcompounds of the formula II, to their salts, to their N-oxides. In thecompounds of the formula II, preference is given to the uses of thosecompounds, wherein X² in formula II is OR^(2a) or SR^(2a). In thesecompounds R^(2a) is preferably C₁-C₆-alkyl, C₃-C₆-alkenyl,C₃-C₆-alkynyl, C₃-C₆-cycloalkylmethyl or C₁-C₄-alkoxy-C₁-C₁₀-alkyl.Another embodiment relates to the methods and uses of compounds of theformula II, wherein X² is NR^(2b)R^(2c). In these compounds R^(2b) andR^(e) are preferably selected, independently of each other, fromC₁-C₆-alkyl, C₃-C₆-cycloalkylmethyl or C₁-C₄-alkoxy-C₁-C₁₀-alkyl orR^(2b) and R^(2c), together with the nitrogen atom to which they areattached, form a saturated, nitrogen-bound 5- or 6-membered heterocyclewhich may comprise a further heteroatom selected from O, S and N, e.g.NR^(2b)R^(2c) being 1-pyrrolidinyl, 1-piperidinyl, 1-piperazinyl,4-morpholinyl or 4-thiomorpholinyl.

In the methods and uses of the compounds according to the presentinvention, preference is given to the methods and uses of compoundswherein R² in formulae I and II is selected from hydrogen, methyl,difluoromethyl, trifluoromethyl, methoxy, difluoromethoxy andtrifluoromethoxy.

In the methods and uses of the compounds according to the presentinvention, preference is given to the methods and uses of compounds,wherein R³ in formulae I and II is selected from hydrogen, methyl,difluoromethyl, trifluoromethyl, methoxy, difluoromethoxy andtrifluoromethoxy.

In particular, at least one of the radicals R² or R³ in formulae I andII is hydrogen. A very preferred embodiment of the invention relates tothe methods and uses of compounds of the formulae I and II and to theirsalts, wherein both R² and R³ are hydrogen.

Another preferred embodiment of the invention relates to the methods anduses of compounds of the formulae I and II and to their salts and totheir N-oxides, wherein R² is hydrogen and R³ is selected from hydrogen,methyl, difluoromethyl, trifluoromethyl, methoxy, difluoromethoxy andtrifluoromethoxy. Another preferred embodiment of the invention relatesto the methods and uses of compounds of the formulae I and II and totheir salts, wherein R³ is hydrogen and R² is selected from hydrogen,methyl, difluoro-methyl, trifluoromethyl, methoxy, difluoromethoxy andtrifluoromethoxy.

A preferred embodiment of the invention relates to the methods and usesof compounds of the formulae I and II, to their salts, to theirN-oxides, wherein A is a radical A1a. Amongst these, preference is givento the methods and uses of such preferred compounds of formula I,wherein X¹, R¹, R² and R³ are as defined above and in particular haveone of the preferred meanings.

Preference is given to the methods and uses of such preferred compoundsof formula I and II, wherein A is a radical A1a, Z is O, either R^(41a)or R^(51a) is hydrogen and the remaining radical is preferably selectedfrom hydrogen, halogen, CN, C₁-C₁₀-alkyl, C₃-C₁₀-cycloalkyl,C₂-C₁₀-alkenyl and C₂-C₁₀-alkynyl, wherein the aliphatic or cyclicmoieties in the 4 last mentioned radicals may be unsubstituted, may bepartially or fully halogenated or may carry 1 or 2 identical ordifferent substituents R^(y). In particular, preference is given to themethods and uses of compounds of formulae I wherein A is a radical A1a,Z is O, either R^(41a) or R^(51a) is hydrogen and the remaining radicalR^(41a) or R^(51a) is selected from hydrogen, halogen, CN,C₁-C₄-haloalkyl, C₃-C₆-cycloalkyl and C₃-C₆-halocycloalkyl. Morepreferably, the remaining radical R^(41a) or R^(51a) in A1a is selectedfrom hydrogen, methyl, ethyl, propyl, CHCF₂, CF₃, Cl, Br.

Preference is also given to the methods and uses of such preferredcompounds of formula I and II, wherein A is a radical A1a, Z is S,R^(41a) and R^(51a) are independently from each other selected fromhydrogen, halogen, CN, C₁-C₁₀-alkyl, C₃-C₁₀-cycloalkyl, C₂-C₁₀-alkenyland C₂-C₁₀-alkynyl, wherein the aliphatic or cyclic moieties in the 4last mentioned radicals may be unsubstituted, may be partially or fullyhalogenated or may carry 1 or 2 identical or different substituentsR^(y). In particular, preference is given to the methods and uses ofcompounds of formulae I wherein A is a radical A1a, Z is S, R^(41a) andR^(51a) are independently from each other selected from hydrogen,halogen, CN, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₃-C₆-cycloalkyl andC₃-C₆-halocycloalkyl. More preferably R^(41a) or R^(51a) are selectedfrom hydrogen, methyl, ethyl, propyl, CHCF₂, CF₃, Cl, Br.

A preferred embodiment of the invention relates to the methods and usesof compounds of the formulae I and II, to their salts, to theirN-oxides, wherein A is a radical A1. Amongst these, preference is givento the methods and uses of such preferred compounds of formula I,wherein X¹, R¹, R² and R³ are as defined above and in particular haveone of the preferred meanings.

Preferably, at least one or both of the radicals R⁴¹ and R⁵¹ arehydrogen. In particular, R⁴¹ and R⁵¹ are independently selected fromhalogen, CN, C₁-C₁₀-alkyl, C₃-C₁₀-cycloalkyl, C₂-C₁₀-alkenyl andC₂-C₁₀-alkynyl, wherein the aliphatic or cyclic moieties in the 4 lastmentioned radicals may be unsubstituted, may be partially or fullyhalogenated or may carry 1 or 2 identical or different substituentsR^(y). Preferably, either R⁴¹ or R⁵¹ is selected from halogen, CN,C₃-C₁₀-cycloalkyl, C₂-C₁₀-alkenyl and C₂-C₁₀-alkynyl, wherein thealiphatic or cyclic moieties in the 4 last mentioned radicals may beunsubstituted, may be partially or fully halogenated or may carry 1 or 2identical or different substituents R^(y), while the remaining radicalR⁴¹ or R⁵¹ is hydrogen or halogen, in particular hydrogen. Morepreferably, R⁴¹ and R⁵¹ are selected from halogen, CN, C₁-C₄-haloalkyl,C₃-C₆-cycloalkyl and C₃-C₆-halocycloalkyl, and most preferably from CH₃,CH₂CH₃, CHCF₂, CF₃, Cl, Br.

In the methods and uses of compounds of the formulae I and II, wherein Ais a radical A1, R⁶¹ is preferably selected from the group consisting ofC₁-C₁₀-alkyl, C₃-C₁₀-cycloalkyl, C₃-C₁₀-halocycloalkyl,C₃-C₁₀-cycloalkylmethyl, C₃-C₁₀-halocycloalkylmethyl, C₂-C₁₀-alkenyl,C₂-C₁₀-haloalkenyl, C₁-C₄-alkoxy-C₁-C₁₀-alkyl, phenyl, benzyl,phenoxy-methyl, 5- or 6-membered hetaryl 5- or 6-membered hetarylmethylwherein the (hetero)aromatic ring of the 5 last mentioned radicals maybe unsubstituted or may carry 1, 2, 3, 4 or 5 identical or differentsubstituents R^(x) which are as defined above and preferably selectedfrom halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy,C₁-C₄-haloalkoxy, C₁-C₄-alkylsulfonyl, and C₁-C₄-haloalkylsulfonyl. Morepreferably R⁵¹ is C₁-C₄-alkyl or C₁-C₄-haloalkyl, in particular methyl,ethyl, n-propyl, isopropyl, Butyl, iso-butyl, sec-butyl, difluoromethyl,trifluoromethyl, 2-fluoroethyl, 2,2-difluoroethyl and2,2,2-trifluoroethyl. In particular, more preferably are the methods anduses of compounds of the formulae I, wherein A is a radical A1, and R⁶¹is more preferably selected from hydrogen, methyl, ethyl, propyl, butyl,iso-butyl, sec-butyl, 2,2,2-trifluoroethyl.

Examples of such radicals of formula A1a or A1 are hereunder listed

Examples of suitable radicals A are the radicals numbered A1a1 to A1a63which are radicals of the formulae Ala wherein Z is S, R^(41a) andR^(51a) are as defined in one row of the following Table A (radicalsA1a1 to A1a63):

TABLE A Radical A1a R^(51a) R^(41a) A1a1 Me H A1a2 Et H A1a3 Pr H A1a4CHF₂ H A1a5 CF₃ H A1a6 Cl H A1a7 Br H A1a8 H Me A1a9 Me Me A1a10 Et MeA1a11 Pr Me A1a12 CHF₂ Me A1a13 CF₃ Me A1a14 Cl Me A1a15 Br Me A1a16 HEt A1a17 Me Et A1a18 Et Et A1a19 Pr Et A1a20 CHF₂ Et A1a21 CF₃ Et A1a22Cl Et A1a23 Br Et A1a24 H Pr A1a25 Me Pr A1a26 Et Pr A1a27 Pr Pr A1a28CHF₂ Pr A1a29 CF₃ Pr A1a30 Cl Pr A1a31 Br Pr A1a32 H CHF₂ A1a33 Me CHF₂A1a34 Et CHF₂ A1a35 Pr CHF₂ A1a36 CHF₂ CHF₂ A1a37 CF₃ CHF₂ A1a38 Cl CHF₂A1a39 Br CHF₂ A1a40 H CF₃ A1a41 Me CF₃ A1a42 Et CF₃ A1a43 Pr CF₃ A1a44CHF₂ CF₃ A1a45 CF₃ CF₃ A1a46 Cl CF₃ A1a47 Br CF₃ A1a48 H Cl A1a49 Me ClA1a50 Et Cl A1a51 Pr Cl A1a52 CHF₂ Cl A1a53 CF₃ Cl A1a54 Cl Cl A1a55 BrCl A1a56 H Br A1a57 Me Br A1a58 Et Br A1a59 Pr Br A1a60 CHF₂ Br A1a61CF₃ Br A1a62 Cl Br A1a63 Br Brand wherein Me=CH₃; Et=CH₂Me; Pr=(CH₂)₂CH₃.

Further radicals which may be used in hereunder are as followingdefined:

Bu=(CH₂)₃CH₃; iBu=CH₂CH(CH₃)₂; sBu=CHCH₃CH₂CH₃.

Analog to the above listed Table A, further examples of suitableradicals A are the radicals of the formulae Ala numbered A1a64 to A1a78wherein Z is O and R^(41a), R^(51a) for each radical have the meaning ofone line in Table A, with the proviso that either R^(41a) or R^(51a) ishydrogen.

Analog to the above listed Table A, further examples of suitableradicals A are the radicals of the formulae A1 numbered A1b1 to A1b63wherein Z is O and R⁴¹, R⁵¹ for each radical have the meaning of oneline in Table A in analogy to respectively R^(41a), R^(51a).

Analog to the above listed Table A, further examples of suitableradicals A are the radicals of the formulae A1 numbered A1b64 to A1b127wherein Z is S and R⁴¹, R⁵¹ for each radical have the meaning of oneline in Table A in analogy to respectively R^(41a), R^(51a).

Analog to the above listed Table A, further examples of suitableradicals A are the radicals of the formulae A1 numbered A1b128 to A1b191wherein Z is NH and R⁴¹, R⁵¹ for each radical have the meaning of oneline in Table A in analogy to respectively R^(41a), R^(51a).

Analog to the above listed Table A, further examples of suitableradicals A are the radicals of the formulae A1 numbered A1b192 to A1b255wherein Z is N—CH_(s) and R⁴¹, R⁵¹ for each radical have the meaning ofone line in Table A in analogy to respectively R^(41a), R^(51a).

Analog to the above listed Table A, further examples of suitableradicals A are the radicals of the formulae A1 numbered A1b256 to A1b319wherein Z is N—CH₂CH₃ and R⁴¹, R⁵¹ for each radical have the meaning ofone line in Table A in analogy to respectively R^(41a), R^(51a).

Analog to the above listed Table A, further examples of suitableradicals A are the radicals of the formulae A1 numbered A1b320 to A1b383wherein Z is N—Pr and R⁴¹, R⁵¹ for each radical have the meaning of oneline in Table A in analogy to respectively R^(41a), R^(51a).

Analog to the above listed Table A, further examples of suitableradicals A are the radicals of the formulae A1 numbered A1b384 to A1b447wherein Z is N-Bu and R⁴¹, R⁵¹ for each radical have the meaning of oneline in Table A in analogy to respectively R^(41a), R^(51a).

Analog to the above listed Table A, further examples of suitableradicals A are the radicals of the formulae A1 numbered A1b448 to A1b511wherein Z is N-iBu and R⁴¹, R⁵¹ for each radical have the meaning of oneline in Table A in analogy to respectively R^(41a), R^(51a).

Analog to the above listed Table A, further examples of suitableradicals A are the radicals of the formulae A1 numbered A1b512 to A1b575wherein Z is N-sBu and R⁴¹, R⁵¹ for each radical have the meaning of oneline in Table A in analogy to respectively R^(41a), R^(51a).

Analog to the above listed Table A, further examples of suitableradicals A are the radicals of the formulae A1 numbered A1b576 to A1b639wherein Z is N—CH₂CF₃ and R⁴¹, R⁵¹ for each radical have the meaning ofone line in Table A in analogy to respectively R^(41a), R^(51a).

A further embodiment of the invention relates to the methods and uses ofcompounds of the formulae I and II, to their salts, wherein A is aradical A2a. Amongst these, preference is given to compounds of theformula I, wherein X¹, R¹, R² and R³ are as defined above and inparticular have one of the preferred meanings.

In the methods and uses of compounds of the formulae I and II, wherein Ais a radical A2a, R^(42a) is preferably selected from the groupconsisting of hydrogen, halogen, NO₂, C₁-C₁₀-alkyl, C₃-C₁₀-cycloalkyl,C₅-C₁₀-cycloalkenyl, C₃-C₁₀-cycloalkylmethyl, C₂-C₁₀-alkenyl,C₂-C₁₀-alkynyl, wherein the aliphatic or cyclic moieties in the 6 lastmentioned radicals may be unsubstituted, may be partially or fullyhalogenated or may carry 1, 2 or 3 identical or different substituentsR^(y), OR^(a), C(Y)R^(b), C(Y)OR^(c), S(O)_(m)R^(d), NR^(e)R^(f),C(Y)NR^(g)R^(h), phenyl, phenyl-C₁-C₄-alkyl, phenoxy-C₁-C₄-alkyl,5-membered hetaryl and heterocyclyl-C₁-C₄-alkyl wherein heterocyclyl andthe aromatic ring of the 5 last mentioned radicals may be unsubstitutedor may carry 1, 2, 3, 4 or 5 identical or different substituents R^(x).Most preferably, R^(42a) is selected from halogen, C₁-C₄-alkyl,C₁-C₄-haloalkyl, C₃-C₆-cycloalkyl and C₃-C₆-halocycloalkyl, and mostpreferably from CH₃, CH₂CH₃, CHCF₂, CF₃, Cl, Br.

In the methods and uses of compounds of the formulae I and II, wherein Ais a radical A2a, R^(52a) is preferably selected from the group asrecited hereunder for the radical R⁵².

A further embodiment of the invention relates to the methods and uses ofcompounds of the formulae I and II, to their salts, wherein A is aradical A2. Amongst these, preference is given to compounds of theformula I, wherein X¹, R¹, R² and R³ are as defined above and inparticular have one of the preferred meanings.

In the methods and uses of compounds of the formulae I and II, wherein Ais a radical A2, R⁴² is preferably selected from hydrogen, halogen, CN,C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₃-C₁₀-cycloalkyl, C₃-C₁₀-halocycloalkyland phenyl which may be unsubstituted or may carry 1, 2, 3, 4 or 5identical or different substituents R^(x) which are as defined above andwhich are preferably selected from halogen, C₁-C₄-alkyl,C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylsulfonyl,and C₁-C₄-haloalkylsulfonyl. In particular, R⁴² is selected fromhydrogen, halogen, CN, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₃-C₆-cycloalkyland C₃-C₆-halocycloalkyl, and more preferably from and most preferablyfrom CH₃, CH₂CH₃, CHCF₂, CF₃, Cl, Br.

In the methods and uses of compounds of the formulae I and II, wherein Ais a radical A2 or A2a, R⁵² or R^(52a) is preferably selected from thegroup consisting of hydrogen, halogen, C₁-C₁₀-alkyl, C₁-C₁₀-haloalkyl,C₃-C₁₀-cycloalkyl, C₃-C₁₀-halocycloalkyl, C₃-C₁₀-cycloalkylmethyl,C₃-C₁₀-halocycloalkylmethyl, C₂-C₁₀-alkenyl, C₂-C₁₀-haloalkenyl,C₁-C₄-alkoxy-C₁-C₁₀-alkyl, phenyl, benzyl, phenoxy-methyl, 5- or6-membered hetaryl, 5- or 6-membered hetarylmethyl wherein the(hetero)aromatic ring of the 5 last mentioned radicals may beunsubstituted or may carry 1, 2, 3, 4 or 5 identical or differentsubstituents R^(x) which are as defined above and preferably selectedfrom halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy,C₁-C₄-haloalkoxy, C₁-C₄-alkylsulfonyl, and C₁-C₄-haloalkylsulfonyl. Morepreferably R⁵² is selected from the group consisting of hydrogen,halogen, CN, C₁-C₁₀-alkyl, C₁-C₁₀-haloalkyl, C₃-C₁₀-cycloalkyl,C₃-C₁₀-halocycloalkyl, C₃-C₁₀-cycloalkylmethyl,C₃-C₁₀-halocycloalkylmethyl, C₂-C₁₀-alkenyl, C₂-C₁₀-haloalkenyl andC₁-C₄-alkoxy-C₁-C₁₀-alkyl. Most preferably R⁵² or R^(52a) is hydrogen,halogen, C₁-C₄-alkyl or C₁-C₄-haloalkyl, in particular methyl, ethyl,n-propyl, isopropyl, difluoromethyl, trifluoromethyl and2,2,2-trifluoroethyl, Br, Cl.

In the methods and uses of compounds of the formulae I and II, wherein Ais a radical A2, R⁶² is preferably selected from the group consisting ofC₁-C₁₀-alkyl, C₁-C₁₀-haloalkyl, C₃-C₁₀-cycloalkyl,C₃-C₁₀-halocycloalkyl, C₃-C_(1D)-cycloalkylmethyl,C₃-C₁₀-halocycloalkylmethyl, C₂-C₁₀-alkenyl, C₂-C₁₀-haloalkenyl,C₁-C₄-alkoxy-C₁-C₁₀-alkyl, phenyl, benzyl and phenoxymethyl wherein thearomatic ring of the 3 last mentioned radicals may be unsubstituted ormay carry 1, 2, 3, 4 or 5 identical or different substituents R^(x)which is as defined above and more preferably selected from halogen,C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy,C₁-C₄-alkylsulfonyl, and C₁-C₄-haloalkylsulfonyl. More preferably R⁶² isC₁-C₄-alkyl or C₁-C₄-haloalkyl, in particular methyl, ethyl, n-propyl,isopropyl, Butyl, iso-butyl, sec-butyl, difluoromethyl, trifluoromethyl,2-fluoroethyl, 2,2-difluoroethyl and 2,2,2-trifluoroethyl. Inparticular, more preferably are the methods and uses of compounds of theformulae I, wherein A is a radical A1, and R⁶² is more preferablyselected from hydrogen, methyl, ethyl, propyl, butyl, iso-butyl,sec-butyl, 2,2,2-trifluoroethyl.

Examples of such radicals of formula A2a or A2 are hereunder listed:

Analog to the above listed Table A, further examples of suitableradicals A are the radicals of the formulae A2a numbered A2a1 to A2a63wherein Z is O and R^(42a), R^(52a) for each radical have the meaning ofone line in Table A in analogy to respectively R^(41a), R^(51a).

Analog to the above listed Table A, further examples of suitableradicals A are the radicals of the formulae A2a numbered A2a64 to A2a127wherein Z is S and R^(42a), R^(52a) for each radical have the meaning ofone line in Table A in analogy to respectively R^(41a), R^(51a).

Analog to the above listed Table A, further examples of suitableradicals A are the radicals of the formulae A2 numbered A2b1 to A2b63wherein Z is O and R⁴², R⁵² for each radical have the meaning of oneline in Table A in analogy to respectively R^(41a), R^(51a).

Analog to the above listed Table A, further examples of suitableradicals A are the radicals of the formulae A2 numbered A2b64 to A2b127wherein Z is S and R⁴², R⁵² for each radical have the meaning of oneline in Table A in analogy to respectively R^(41a), R^(51a).

Analog to the above listed Table A, further examples of suitableradicals A are the radicals of the formulae A2 numbered A2b128 to A2b191wherein Z is NH and R⁴², R⁵² for each radical have the meaning of oneline in Table A in analogy to respectively R^(41a), R^(51a).

Analog to the above listed Table A, further examples of suitableradicals A are the radicals of the formulae A2 numbered A2b192 to A2b255wherein Z is NCH₃ and R⁴², R⁵² for each radical have the meaning of oneline in Table A in analogy to respectively R^(41a), R^(51a).

Analog to the above listed Table A, further examples of suitableradicals A are the radicals of the formulae A2 numbered A2b256 to A2b319wherein Z is N-Et and R⁴², R⁵² for each radical have the meaning of oneline in Table A in analogy to respectively R^(41a), R^(51a).

Analog to the above listed Table A, further examples of suitableradicals A are the radicals of the formulae A2 numbered A2b320 to A2b383wherein Z is N—Pr and R⁴², R⁵² for each radical have the meaning of oneline in Table A in analogy to respectively R^(41a), R^(51a).

Analog to the above listed Table A, further examples of suitableradicals A are the radicals of the formulae A2 numbered A2b384 to A2b447wherein Z is N-Bu and R⁴², R⁵² for each radical have the meaning of oneline in Table A in analogy to respectively R^(41a), R^(51a).

Analog to the above listed Table A, further examples of suitableradicals A are the radicals of the formulae A2 numbered A2b448 to A2b511wherein Z is N-iBu and R⁴², R⁵² for each radical have the meaning of oneline in Table A in analogy to respectively R^(41a), R^(51a).

Analog to the above listed Table A, further examples of suitableradicals A are the radicals of the formulae A2 numbered A2b512 to A2b575wherein Z is N-sBu and R⁴², R⁵² for each radical have the meaning of oneline in Table A in analogy to respectively R^(41a), R^(51a).

Analog to the above listed Table A, further examples of suitableradicals A are the radicals of the formulae A2 numbered A2b576 to A2b639wherein Z is N—CH₂CF₃ and R⁴², R⁵² for each radical have the meaning ofone line in Table A in analogy to respectively R^(41a), R^(51a).

A further embodiment of the invention relates to the methods and uses ofcompounds of the formulae I and II, to their salts, wherein A is aradical A3. Amongst these, preference is given to compounds of theformula I, wherein X¹, R¹, R² and R³ are as defined above and inparticular have one of the preferred meanings.

In the methods and uses of compounds of the formulae I and II, wherein Ais a radical A3a, R^(43a) is preferably selected from hydrogen, halogen,CN, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₃-C₁₀-cycloalkyl,C₃-C₁₀-halocycloalkyl and phenyl which may be unsubstituted or may carry1, 2, 3, 4 or 5 identical or different substituents R^(x) which are asdefined above and which are preferably selected from halogen,C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy,C₁-C₄-alkylsulfonyl, and C₁-C₄-haloalkylsulfonyl. In particular, R^(43a)is selected from hydrogen, halogen, CN, C₁-C₄-alkyl, C₁-C₄-haloalkyl,C₃-C₆-cycloalkyl and C₃-C₆-halocycloalkyl, and more preferably from CH₃,CH₂CH₃, CHCF₂, CF₃, Cl, Br.

In the methods and uses of compounds of the formulae I and II, wherein Ais a radical A3a, R^(53a) is preferably selected from the group asrecited hereunder for the radical R⁵³.

A further embodiment of the invention relates to the methods and uses ofcompounds of the formulae I and II, to their salts, wherein A is aradical A3. Amongst these, preference is given to compounds of theformula I, wherein X¹, R¹, R² and R³ are as defined above and inparticular have one of the preferred meanings.

In the methods and uses of compounds of the formulae I and II, wherein Ais a radical A3, R⁴³ is preferably selected from hydrogen, halogen, CN,C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₃-C₁₀-cycloalkyl, C₃-C₁₀-halocycloalkyland phenyl which may be unsubstituted or may carry 1, 2, 3, 4 or 5identical or different substituents R^(x) which are as defined above andwhich are preferably selected from halogen, C₁-C₄-alkyl,C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, C₁-C₄-alkylsulfonyl,and C₁-C₄-haloalkylsulfonyl. In particular, R⁴³ is selected fromhydrogen, halogen, CN, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₃-C₆-cycloalkyland C₃-C₆-halocycloalkyl, and more preferably from and most preferablyfrom CH₃, CH₂CH₃, CHCF₂, CF₃, Cl, Br.

In the methods and uses of compounds of the formulae I and II, wherein Ais a radical A3 or A3a, R⁵³ or R^(53a) is preferably selected from thegroup consisting of hydrogen, halogen, C₁-C₁₀-alkyl, C₃-C₁₀-cycloalkyl,C₃-C₁₀-halocycloalkyl, C₃-C₁₀-cycloalkylmethyl,C₃-C₁₀-halocycloalkylmethyl, C₂-C₁₀-alkenyl, C₂-C₁₀-haloalkenyl,C₁-C₄-alkoxy-C₁-C₁₀-alkyl, phenyl, benzyl, phenoxy-methyl, 5- or6-membered hetaryl, 5- or 6-membered hetarylmethyl wherein the(hetero)aromatic ring of the 5 last mentioned radicals may beunsubstituted or may carry 1, 2, 3, 4 or 5 identical or differentsubstituents R^(x) which are as defined above and preferably selectedfrom halogen, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy,C₁-C₄-haloalkoxy, C₁-C₄-alkylsulfonyl, and C₁-C₄-haloalkylsulfonyl. Morepreferably R⁵³ is selected from the group consisting of hydrogen,halogen, CN, C₁-C₁₀-alkyl, C₁-C₁₀-haloalkyl, C₃-C₁₀-cycloalkyl,C₃-C₁₀-halocycloalkyl, C₃-C₁₀-cycloalkylmethyl,C₃-C₁₀-halocycloalkylmethyl, C₂-C₁₀-alkenyl, C₂-C₁₀-haloalkenyl andC₁-C₄-alkoxy-C₁-C₁₀-alkyl. Most preferably R⁵³ is hydrogen, halogen,C₁-C₄-alkyl or C₁-C₄-haloalkyl, in particular methyl, ethyl, n-propyl,isopropyl, difluoromethyl, trifluoromethyl or 2,2,2-trifluoroethyl, andmore preferably from CH₃, CH₂CH₃, CHCF₂, CF₃, Cl, Br.

In the methods and uses of compounds of the formulae I and II, wherein Ais a radical A2, R⁶³ is preferably selected from the group consisting ofC₁-C₁₀-alkyl, C₁-C₁₀-haloalkyl, C₃-C₁₀-cycloalkyl,C₃-C₁₀-halocycloalkyl, C₃-C₁₀-cycloalkylmethyl,C₃-C₁₀-halocycloalkylmethyl, C₂-C₁₀-alkenyl, C₂-C₁₀-haloalkenyl,C₁-C₄-alkoxy-C₁-C₁₀-alkyl, phenyl, benzyl and phenoxymethyl wherein thearomatic ring of the 3 last mentioned radicals may be unsubstituted ormay carry 1, 2, 3, 4 or 5 identical or different substituents R^(x)which is as defined above and more preferably selected from halogen,C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy,C₁-C₄-alkylsulfonyl, and C₁-C₄-haloalkylsulfonyl. More preferably R⁶³ isC₁-C₄-alkyl or C₁-C₄-haloalkyl, in particular methyl, ethyl, n-propyl,isopropyl, Butyl, iso-butyl, sec-butyl, difluoromethyl, trifluoromethyl,2-fluoroethyl, 2,2-difluoroethyl and 2,2,2-trifluoroethyl. Inparticular, more preferably are the methods and uses of compounds of theformulae I, wherein A is a radical A1, and R⁶³ is more preferablyselected from hydrogen, methyl, ethyl, propyl, butyl, iso-butyl,sec-butyl, 2,2,2-trifluoroethyl.

Examples of such radicals of formula A3a or A3 are hereunder listed:

Analog to the above listed Table A, further examples of suitableradicals A are the radicals of the formulae A3a numbered A3a1 to A3a63wherein Z is O and R^(43a), R^(53a) for each radical have the meaning ofone line in Table A in analogy to respectively R^(41a), R^(51a).

Analog to the above listed Table A, further examples of suitableradicals A are the radicals of the formulae A3a numbered A3a64 to A3a127wherein Z is S and R^(43a), R^(53a) for each radical have the meaning ofone line in Table A in analogy to respectively R^(41a), R^(51a).

Analog to the above listed Table A, further examples of suitableradicals A are the radicals of the formulae A3 numbered A3b1 to A3b63wherein Z is O and R⁴³, R⁵³ for each radical have the meaning of oneline in Table A.

Analog to the above listed Table A, further examples of suitableradicals A are the radicals of the formulae A3 numbered A3b64 to A3b127wherein Z is S and R⁴³, R⁵³ for each radical have the meaning of oneline in Table A in analogy to respectively R^(41a), R^(51a).

Analog to the above listed Table A, further examples of suitableradicals A are the radicals of the formulae A3 numbered A3b128 to A3b191wherein Z is NH and R⁴³, R⁵³ for each radical have the meaning of oneline in Table A in analogy to respectively R^(41a), R^(51a).

Analog to the above listed Table A, further examples of suitableradicals A are the radicals of the formulae A3 numbered A3b192 to A3b255wherein Z is NCH₃ and R⁴³, R⁵³ for each radical have the meaning of oneline in Table A in analogy to respectively R^(41a), R^(51a).

Analog to the above listed Table A, further examples of suitableradicals A are the radicals of the formulae A3 numbered A3b256 to A3b319wherein Z is N-Et and R⁴³, R⁵³ for each radical have the meaning of oneline in Table A in analogy to respectively R^(41a), R^(51a).

Analog to the above listed Table A, further examples of suitableradicals A are the radicals of the formulae A3 numbered A3b320 to A3b383wherein Z is N—Pr and R⁴³, R⁵³ for each radical have the meaning of oneline in Table A in analogy to respectively R^(41a), R^(51a).

Analog to the above listed Table A, further examples of suitableradicals A are the radicals of the formulae A3 numbered A3b384 to A3b447wherein Z is N-Bu and R⁴³, R⁵³ for each radical have the meaning of oneline in Table A in analogy to respectively R^(41a), R^(51a).

Analog to the above listed Table A, further examples of suitableradicals A are the radicals of the formulae A3 numbered A3b448 to A3b511wherein Z is N-iBu and R⁴³, R⁵³ for each radical have the meaning of oneline in Table A in analogy to respectively R^(41a), R^(51a).

Analog to the above listed Table A, further examples of suitableradicals A are the radicals of the formulae A3 numbered A3b4512 toA3b575 wherein Z is N-sBu and R⁴³, R⁵³ for each radical have the meaningof one line in Table A in analogy to respectively R^(41a), R^(51a).

Analog to the above listed Table A, further examples of suitableradicals A are the radicals of the formulae A3 numbered A3b575 to A3b639wherein Z is N—CH₂CF₃ and R⁴³, R⁵³ for each radical have the meaning ofone line in Table A in analogy to respectively R^(41a), R^(51a).

Apart from that, X³ is preferably a lone pair. Compounds of the formulaeI or II, wherein X³ is O are also referred to as N-oxides of compounds Ior II.

Apart from that, the variables Y, R^(a), R^(b), R^(c), R^(d), R^(e),R^(f), R^(g), R^(h), R^(x) and R^(y), independently of each other,preferably have one of the following meanings:

-   Y is preferably O;-   R^(a), R^(b), R^(c) are independently of each other selected from    hydrogen, C₁-C₄-alkyl and C₁-C₄-haloalkyl;-   R^(d) is selected from C₁-C₄-alkyl and C₁-C₄-haloalkyl;-   R^(e), R^(f) are independently of each other selected from hydrogen,    C₁-C₄-alkyl, or-   R^(e) and R^(f) together with the nitrogen atom to which they are    bound form a 5- or 6-membered, saturated heterocycle, which may    carry a further heteroatom being selected from O, S and N as a ring    member atom, e.g. pyrrolidin-1-yl, piperidin-1-yl, morpholin-4-yl,    piperazin-1-yl or 4-methylpiperazin-1-yl;-   R^(e), R^(h), R^(i) are independently of each other selected from    hydrogen and C₁-C₄-alkyl;-   R^(x) is selected from the group consisting of halogen, cyano,    nitro, C₁-C₄-alkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy,    C₁-C₄-alkylsulfonyl and C₁-C₄-haloalkylsulfonyl;-   R^(y) is selected from C₁-C₄-alkoxy, C₃-C₆-cycloalkyl and phenyl.

A very preferred embodiment of the invention relates to the methods anduses of compounds of the formula I and to their salts, wherein X¹ is Oand X³ is a lone pair. These compounds are hereinafter also referred toas compounds Ia.

In formula Ia, the variables A, R¹, R² and R³ are as defined herein.Amongst the compounds of the formula Ia, preference is given to thosecompounds, wherein A is a radical Ala or A1, e.g. a radical, selectedfrom the 5-membered heterocyclic radicals numbered A1a1 to A1.a78.Amongst the compounds of the formula Ia, preference is given to thosecompounds, wherein at least one of the radicals R¹, R² and R³,preferably at least two of the radicals R¹, R² and R³, and morepreferably all of the radicals R¹, R² and R³ have one of the preferredmeanings.

A particular preferred embodiment relates to the methods and uses ofcompounds of the formula Ia and to their salts, wherein

-   A is a radical A1a, as defined herein, in particular a radical A1,    wherein R^(41a), R^(51a) have the preferred meanings, in particular    a radical selected from the radicals A1a64 to A1.78;-   R¹ has the meaning as defined in each example of the Tables 1 to 72    hereunder listed;-   R² is selected from hydrogen, methyl, difluoromethyl,    trifluoromethyl, methoxy, difluoromethoxy and trifluoromethoxy; and-   R³ is selected from hydrogen, methyl, difluoromethyl,    trifluoromethyl, methoxy, difluoromethoxy and trifluoromethoxy; and    wherein preferably one or both radicals R² and R³ are hydrogen.

Examples of compounds of this particular preferred embodiment of methodsand uses of such compounds are the compounds given in the followingtables 1 to 72.

-   Table 1: Compounds of the formula Ia and their salts, wherein R¹, R²    and R³ are hydrogen and wherein A is selected from the radicals A1a1    to A1a78.-   Table 2: Compounds of the formula Ia and their salts, wherein R¹ is    CH₃, R² and R³ are hydrogen and wherein A is selected from the    radicals A1a1 to A1a78.-   Table 3: Compounds of the formula Ia and their salts, wherein R¹ is    CH₂CH₃, R² and R³ are hydrogen and wherein A is selected from the    radicals A1a1 to A1a78.-   Table 4: Compounds of the formula Ia and their salts, wherein R¹ is    propyl, R² and R³ are hydrogen and wherein A is selected from the    radicals A1a1 to A1a78.-   Table 5: Compounds of the formula Ia and their salts, wherein R¹ is    iso-propyl, R² and R³ are hydrogen and wherein A is selected from    the radicals A1a1 to A1a78.-   Table 6: Compounds of the formula Ia and their salts, wherein R¹ is    butyl, R² and R³ are hydrogen and wherein A is selected from the    radicals A1a1 to A1a78.-   Table 7: Compounds of the formula Ia and their salts, wherein R¹ is    iso-butyl, R² and R³ are hydrogen and wherein A is selected from the    radicals A1a1 to A1a78.-   Table 8: Compounds of the formula Ia and their salts, wherein R¹ is    tert-butyl, R² and R³ are hydrogen and wherein A is selected from    the radicals A1a1 to A1a78.-   Table 9: Compounds of the formula Ia and their salts, wherein R¹ is    CH₂C(CH)₃, R² and R³ are hydrogen and wherein A is selected from the    radicals A1a1 to A1a78.-   Table 10: Compounds of the formula Ia and their salts, wherein R¹ is    CH₂═CHCCl₂, R² and R³ are hydrogen and wherein A is selected from    the radicals A1a1 to A1a78.-   Table 11: Compounds of the formula Ia and their salts, wherein R¹ is    CH₂CH═CBr₂, R² and R³ are hydrogen and wherein A is selected from    the radicals A1a1 to A1a78.-   Table 12: Compounds of the formula Ia and their salts, wherein R¹ is    CH₂CH₂Cl, R² and R³ are hydrogen and wherein A is selected from the    radicals A1a1 to A1a78.-   Table 13: Compounds of the formula Ia and their salts, wherein R¹ is    CH₂CH₂F, R² and R³ are hydrogen and wherein A is selected from the    radicals A1a1 to A1a78.-   Table 14: Compounds of the formula Ia and their salts, wherein R¹ is    CH₂CH₂Br, R² and R³ are hydrogen and wherein A is selected from the    radicals A1a1 to A1a78.-   Table 15: Compounds of the formula Ia and their salts, wherein R¹ is    CH₂CHF₂, R² and R³ are hydrogen and wherein A is selected from the    radicals A1a1 to A1a78.-   Table 16: Compounds of the formula Ia and their salts, wherein R¹ is    CH₂CHBr₂, R² and R³ are hydrogen and wherein A is selected from the    radicals A1a1 to A1a78.-   Table 17: Compounds of the formula Ia and their salts, wherein R¹ is    CH₂CHCl₂, R² and R³ are hydrogen and wherein A is selected from the    radicals A1a1 to A1a78.-   Table 18: Compounds of the formula Ia and their salts, wherein R¹ is    CH₂CF₃, R² and R³ are hydrogen and wherein A is selected from the    radicals A1a1 to A1a78.-   Table 19: Compounds of the formula Ia and their salts, wherein R¹ is    CH₂CN, R² and R³ are hydrogen and wherein A is selected from the    radicals A1a1 to A1a78.-   Table 20: Compounds of the formula Ia and their salts, wherein R¹ is    CH₂OCH₃, R² and R³ are hydrogen and wherein A is selected from the    radicals A1a1 to A1a78.-   Table 21: Compounds of the formula Ia and their salts, wherein R¹ is    CH₂OCH₂CH₃, R² and R³ are hydrogen and wherein A is selected from    the radicals A1a1 to A1a78.-   Table 22: Compounds of the formula Ia and their salts, wherein R¹ is    CH₂CH₂CN, R² and R³ are hydrogen and wherein A is selected from the    radicals A1a1 to A1a78.-   Table 23: Compounds of the formula Ia and their salts, wherein R¹ is    CH₂CHCN₂, R² and R³ are hydrogen and wherein A is selected from the    radicals A1a1 to A1a78.-   Table 24: Compounds of the formula Ia and their salts, wherein R¹ is    CH₂CH₂OCH₃, R² and R³ are hydrogen and wherein A is selected from    the radicals A1a1 to A1a78.-   Table 25: Compounds of the formula Ia and their salts, wherein R¹ is    CH₂CH₂OCH₂CH₃, R² and R³ are hydrogen and wherein A is selected from    the radicals A1a1 to A1a78.-   Table 26: Compounds of the formula Ia and their salts, wherein R¹ is    ethylcyclopropane, R² and R³ are hydrogen and wherein A is selected    from the radicals A1a1 to A1a78.-   Table 27: Compounds of the formula Ia and their salts, wherein R¹ is    ethylcyclobutane, R² and R³ are hydrogen and wherein A is selected    from the radicals A1a1 to A1a78.-   Table 28: Compounds of the formula Ia and their salts, wherein R¹ is    2-methyloxetane, R² and R³ are hydrogen and wherein A is selected    from the radicals A1a1 to A1a79.-   Table 29: Compounds of the formula Ia and their salts, wherein R¹ is    3-ethyloxetane, R² and R³ are hydrogen and wherein A is selected    from the radicals A1a1 to A1a78.-   Table 30: Compounds of the formula Ia and their salts, wherein R¹ is    3-methylthietane, R² and R³ are hydrogen and wherein A is selected    from the radicals A1a1 to A1a78.-   Table 31: Compounds of the formula Ia and their salts, wherein R¹ is    3-methylthietane-1,1-dioxide, R² and R³ are hydrogen and wherein A    is selected from the radicals A1a1 to A1a78.-   Table 32: Compounds of the formula Ia and their salts, wherein R¹ is    ethylcyclopentane, R² and R³ are hydrogen and wherein A is selected    from the radicals A1a1 to A1a78.-   Table 33: Compounds of the formula Ia and their salts, wherein R¹ is    2-ethyltetrahydrofuran, R² and R³ are hydrogen and wherein A is    selected from the radicals A1a1 to A1a78.-   Table 34: Compounds of the formula Ia and their salts, wherein R¹ is    3-ethyltetrahydrofuran, R² and R³ are hydrogen and wherein A is    selected from the radicals A1a1 to A1a78.-   Table 35: Compounds of the formula Ia and their salts, wherein R¹ is    methylcyclopropane, R² and R³ are hydrogen and wherein A is selected    from the radicals A1a1 to A1a78.-   Table 36: Compounds of the formula Ia and their salts, wherein R¹ is    ethylcyclobutane, R² and R³ are hydrogen and wherein A is selected    from the radicals A1a1 to A1a78.-   Table 37: Compounds of the formula Ia and their salts, wherein R¹ is    2-methyloxetane, R² and R³ are hydrogen and wherein A is selected    from the radicals A1a1 to A1a78.-   Table 38: Compounds of the formula Ia and their salts, wherein R¹ is    3-methyloxetane, R² and R³ are hydrogen and wherein A is selected    from the radicals A1a1 to A1a78.-   Table 39: Compounds of the formula Ia and their salts, wherein R¹ is    3-methylthietane, R² and R³ are hydrogen and wherein A is selected    from the radicals A1a1 to A1a78.-   Table 40: Compounds of the formula Ia and their salts, wherein R¹ is    3-thietane-1,1-dioxide, R² and R³ are hydrogen and wherein A is    selected from the radicals A1a1 to A1a78.-   Table 41: Compounds of the formula Ia and their salts, wherein R¹ is    cyclopentane, R² and R³ are hydrogen and wherein A is selected from    the radicals A1a1 to A1a78.-   Table 42: Compounds of the formula Ia and their salts, wherein R¹ is    2-methyltetrahydrofuran, R² and R³ are hydrogen and wherein A is    selected from the radicals A1a1 to A1a78.-   Table 43: Compounds of the formula Ia and their salts, wherein R¹ is    tetrahydrofuran, R² and R³ are hydrogen and wherein A is selected    from the radicals A1a1 to A1a78.-   Table 44: Compounds of the formula Ia and their salts, wherein R¹ is    toluene, R² and R³ are hydrogen and wherein A is selected from the    radicals A1a1 to A1a78.-   Table 45: Compounds of the formula Ia and their salts, wherein R¹ is    2-methylfuran, R² and R³ are hydrogen and wherein A is selected from    the radicals A1a1 to A1a78.-   Table 46: Compounds of the formula Ia and their salts, wherein R¹ is    3-methylfuran, R² and R³ are hydrogen and wherein A is selected from    the radicals A1a1 to A1a78.-   Table 47: Compounds of the formula Ia and their salts, wherein R¹ is    2-ethylthiophene, R² and R³ are hydrogen and wherein A is selected    from the radicals A1a1 to A1a78.-   Table 48: Compounds of the formula Ia and their salts, wherein R¹ is    3-methylthiophene, R² and R³ are hydrogen and wherein A is selected    from the radicals A1a1A1a1 to A1a78.-   Table 49: Compounds of the formula Ia and their salts, wherein R¹ is    5-ethylisothiazole, R² and R³ are hydrogen and wherein A is selected    from the radicals A1a1 to A1a78.-   Table 50: Compounds of the formula Ia and their salts, wherein R¹ is    4-ethylisothiazole, R² and R³ are hydrogen and wherein A is selected    from the radicals A1a1 to A1a78.-   Table 51: Compounds of the formula Ia and their salts, wherein R¹ is    3-methylisothiazole, R² and R³ are hydrogen and wherein A is    selected from the radicals A1a1 to A1a78.-   Table 52: Compounds of the formula Ia and their salts, wherein R¹ is    3-methylisoxazole, R² and R³ are hydrogen and wherein A is selected    from the radicals A1a1 to A1a78.-   Table 53: Compounds of the formula Ia and their salts, wherein R¹ is    5-methyloxazole, R² and R³ are hydrogen and wherein A is selected    from the radicals A1a1 to A1a78.-   Table 54: Compounds of the formula Ia and their salts, wherein R¹ is    2-ethyloxazole, R² and R³ are hydrogen and wherein A is selected    from the radicals A1a1 to A1a78.-   Table 55: Compounds of the formula Ia and their salts, wherein R¹ is    5-ethylthiazole, R² and R³ are hydrogen and wherein A is selected    from the radicals A1a1 to A1a78.-   Table 56: Compounds of the formula Ia and their salts, wherein R¹ is    2-ethylthiazole, R² and R³ are hydrogen and wherein A is selected    from the radicals A1a1 to A1a78.-   Table 57: Compounds of the formula Ia and their salts, wherein R¹ is    5-methyl-1H-pyrazole, R² and R³ are hydrogen and wherein A is    selected from the radicals A1a1 to A1a78.-   Table 58: Compounds of the formula Ia and their salts, wherein R¹ is    3-methyl-1H-pyrazole, R² and Ware hydrogen and wherein A is selected    from the radicals A1a1 to A1a78.-   Table 59: Compounds of the formula Ia and their salts, wherein R¹ is    4-ethyl-1-methyl-1-H-pyrazole, R² and R³ are hydrogen and wherein A    is selected from the radicals A1a1 to A1a78.-   Table 60: Compounds of the formula Ia and their salts, wherein R¹ is    5-ethyl-1-methyl-1-H-pyrazole, R² and R³ are hydrogen and wherein A    is selected from the radicals A1a1 to A1a78.-   Table 61: Compounds of the formula Ia and their salts, wherein R¹ is    3-ethyl-1-methyl-1-H-pyrazole, R² and R³ are hydrogen and wherein A    is selected from the radicals A1a1 to A1a78.-   Table 62: Compounds of the formula Ia and their salts, wherein R¹ is    5-methyl-1H-imidazole, R² and R³ are hydrogen and wherein A is    selected from the radicals A1a1 to A1a78.-   Table 63: Compounds of the formula Ia and their salts, wherein R¹ is    4-ethyl-1H-imidazole, R² and R³ are hydrogen and wherein A is    selected from the radicals A1a1 to A1a78.-   Table 64: Compounds of the formula Ia and their salts, wherein R¹ is    3-CH₃—C₆H₄, R² and R³ are hydrogen and wherein A is selected from    the radicals A1a1 to A1a78.-   Table 65: Compounds of the formula Ia and their salts, wherein R¹ is    2-methyl-1H-imidazole, R² and R³ are hydrogen and wherein A is    selected from the radicals A1a1 to A1a78.-   Table 66: Compounds of the formula Ia and their salts, wherein R¹ is    5-ethyl-1-methyl-1-H-imidazole, R² and R³ are hydrogen and wherein A    is selected from the radicals A1a1 to A1a78.-   Table 67: Compounds of the formula Ia and their salts, wherein R¹ is    2-ethyl-1-methyl-1-H-imidazole, R² and R³ are hydrogen and wherein A    is selected from the radicals A1a1 to A1a78.-   Table 68: Compounds of the formula Ia and their salts, wherein R¹ is    1,4-dimethyl-1H-imidazole, R² and R³ are hydrogen and wherein A is    selected from the radicals A1a1 to A1a78.-   Table 69: Compounds of the formula Ia and their salts, wherein R¹ is    2-methyl-4,5-dihydrooxazole, R² and R³ are hydrogen and wherein A is    selected from the radicals A1a1 to A1a78.-   Table 70: Compounds of the formula Ia and their salts, wherein R¹ is    2-ethyl-4,5-dihydrothiazole, R² and R³ are hydrogen and wherein A is    selected from the radicals A1a1 to A1a78.-   Table 71: Compounds of the formula Ia and their salts, wherein R¹ is    2-ethyl-4,5-dihydro-1H-imidazole, R² and R³ are hydrogen and wherein    A is selected from the radicals A1a1 to A1a78.-   Table 72: Compounds of the formula Ia and their salts, wherein R¹ is    2-ethyl-1-methyl-4,5-dihydro-1H-imidazole, R² and R³ are hydrogen    and wherein A is selected from the radicals A1a1 to A1a78.

A further preferred embodiment relates to the methods and uses ofcompounds of the formula Ia and to their salts, wherein

-   A is a radical A1, as defined herein, in particular a radical A1,    wherein R⁴¹, R⁵¹ have the preferred meanings, in particular a    radical A selected from the radicals A1b1 to A1b639;-   R¹ has the meaning as defined in each example of the Tables 1 to 72;-   R² is selected from hydrogen, methyl, difluoromethyl,    trifluoromethyl, methoxy, difluoromethoxy and trifluoromethoxy; and-   R³ is selected from hydrogen, methyl, difluoromethyl,    trifluoromethyl, methoxy, difluoromethoxy and trifluoromethoxy; and    wherein preferably one or both radicals R² and R³ are hydrogen.

Examples of compounds of this particular preferred embodiment of methodsand uses of such compounds are the compounds given in the followingtables 73 to 145.

Tables 73 to 145: Compounds of the formula Ia and the salts and N-oxidesthereof, wherein R² and R³ are hydrogen, A is selected from the radicalsA1b1 to A1b639 and wherein R¹ is as defined in tables 1 to 72.

A further preferred embodiment relates to the methods and uses ofcompounds of the formula Ia and to their salts, wherein

-   A is a radical A2, as defined herein, in particular a radical A2,    wherein R⁴², R⁵² have the preferred meanings, in particular a    radical A selected from the radicals A2b1 to A2b639;-   R¹ has the meaning as defined in each example of the Tables 1 to 72;-   R² is selected from hydrogen, methyl, difluoromethyl,    trifluoromethyl, methoxy, difluoromethoxy and trifluoromethoxy; and-   R³ is selected from hydrogen, methyl, difluoromethyl,    trifluoromethyl, methoxy, difluoromethoxy and trifluoromethoxy; and    wherein preferably one or both radicals R² and R³ are hydrogen.

Examples of compounds of this particular preferred embodiment of methodsand uses of such compounds are the compounds given in the followingtables 146 to 218.

Tables 146 to 218: Compounds of the formula Ia and the salts andN-oxides thereof, wherein R² and R³ are hydrogen, A is selected from theradicals A2b1 to A2b639 and wherein R¹ is as defined in tables 1 to 72.

A further preferred embodiment relates to the methods and uses ofcompounds of the formula Ia and to their salts, wherein

-   A is a radical A3, as defined herein, in particular a radical A3,    wherein R⁴³, R⁵³ have the preferred meanings, in particular a    radical A selected from the radicals A3b1 to A3b639;-   R¹ has the meaning as defined in each example of the Tables 1 to 72;-   R² is selected from hydrogen, methyl, difluoromethyl,    trifluoromethyl, methoxy, difluoromethoxy and trifluoromethoxy; and-   R³ is selected from hydrogen, methyl, difluoromethyl,    trifluoromethyl, methoxy, difluoromethoxy and trifluoromethoxy; and    wherein preferably one or both radicals R² and R³ are hydrogen.

Examples of compounds of this particular preferred embodiment of methodsand uses of such compounds are the compounds given in the followingtables 219 to 291.

Tables 219 to 291: Compounds of the formula Ia and the salts andN-oxides thereof, wherein R² and R³ are hydrogen, A is selected from theradicals A3b1 to A3b639 and wherein R¹ is as defined in tables 1 to 72.

A further preferred embodiment relates to the methods and uses ofcompounds of the formula Ia and to their salts, wherein

-   A is a radical A2a, as defined herein, in particular a radical A2a,    wherein R^(42a), R^(52a) have the preferred meanings, in particular    a radical A selected from the radicals A2a1 to A2a127;-   R¹ has the meaning as defined in each example of the Tables 1 to 72;-   R² is selected from hydrogen, methyl, difluoromethyl,    trifluoromethyl, methoxy, difluoromethoxy and trifluoromethoxy; and-   R³ is selected from hydrogen, methyl, difluoromethyl,    trifluoromethyl, methoxy, difluoromethoxy and trifluoromethoxy; and    wherein preferably one or both radicals R² and R³ are hydrogen.

Examples of compounds of this particular preferred embodiment of methodsand uses of such compounds are the compounds given in the followingtables 292 to 364.

Tables 292 to 364: Compounds of the formula Ia and the salts andN-oxides thereof, wherein R² and R³ are hydrogen, A is selected from theradicals A2a1 to A2a127 and wherein R¹ is as defined in tables 1 to 72.

A further preferred embodiment relates to the methods and uses ofcompounds of the formula Ia and to their salts, wherein

-   A is a radical A3a, as defined herein, in particular a radical A3a,    wherein R^(43a), R^(53a) have the preferred meanings, in particular    a radical A selected from the radicals A3a1 to A3a127;-   R¹ has the meaning as defined in each example of the Tables 1 to 72;-   R² is selected from hydrogen, methyl, difluoromethyl,    trifluoromethyl, methoxy, difluoromethoxy and trifluoromethoxy; and-   R³ is selected from hydrogen, methyl, difluoromethyl,    trifluoromethyl, methoxy, difluoromethoxy and trifluoromethoxy; and    wherein preferably one or both radicals R² and R³ are hydrogen.

Examples of compounds of this particular preferred embodiment of methodsand uses of such compounds are the compounds given in the followingtables 365 to 437.

Tables 365 to 437: Compounds of the formula Ia and the salts andN-oxides thereof, wherein R² and R³ are hydrogen, A is selected from theradicals A3a1 to A3a127 and wherein R¹ is as defined in tables 1 to 72.

The compounds of the formulae I or II can be prepared by the standardmethods of organic chemistry, e.g. by the methods described hereinafteror in the working examples:

The compounds of the formula Ia, wherein X¹ is O and X³ is a lone pair,can be prepared e.g. according to the method depicted in scheme 1 byreacting activated oxazole or thiazole or imidazole or isoxazole orisothiazole carboxylic acid derivative IIa with a 3-aminopyridinecompound III (see e.g. Houben-Weyl: “Methoden der organ. Chemie”[Methods of Organic Chemistry], Georg-Thieme-Verlag, Stuttgart, New York1985, Volume E5, pp. 941-1045). Activated oxazole or thiazole orimidazole or isoxazole or isothiazole carboxylic acid derivatives IIaare, for example, acyl halides, activated esters, anhydrides, acylazides, wherein X is for example chlorine, fluorine, bromine,para-nitrophenoxy, pentafluorophenoxy, N-hydroxysuccinimides,hydroxybenzotriazol-1-yl. In scheme 1, the radicals A, R¹, R² and R³have the meanings mentioned above and in particular the meaningsmentioned as being preferred.

The active compounds of the formula Ia, wherein X¹ is O and X³ is a lonepair, can also be prepared, for example, by reacting the oxazole orthiazole or imidazole or isoxazole or isothiazole carboxylic acid IVwith a 3-aminopyridine compound III in the presence of a coupling agentaccording to scheme 2. In scheme 2, the radicals A, R¹, R² and R³ havethe meanings given above and in particular the meanings given as beingpreferred.

Suitable coupling agents are, for example:

-   -   coupling agents based on carbodiimides, for example        N,N′-dicyclohexylcarbodiimide [J. C. Sheehan, G. P. Hess, J. Am.        Chem. Soc. 1955, 77, 1067],        N-(3-dimethylaminopropyl)-N′-ethylcarbodiimide;    -   coupling agents which form mixed anhydrides with carbonic        esters, for example        2-ethoxy-1-ethoxycarbonyl-1,2-dihydroquinoline [B. Belleau, G.        Malek, J. Amer. Chem. Soc. 1968, 90, 1651],        2-isobutyloxy-1-isobutyloxycarbonyl-1,2-dihydroquinoline [Y.        Kiso, H. Yajima, J. Chem. Soc., Chem. Commun. 1972, 942];    -   coupling agents based on phosphonium salts, for example        (benzotriazol-1-yloxy)tris(dimethylamino)phosphonium        hexafluorophosphate [B. Castro, J. R. Domoy, G. Evin, C. Selve,        Tetrahedron Lett. 1975, 14, 1219],        (benzotriazol-1-yl-oxy)tripyrrolidinophosphonium        hexafluorophosphate [J. Coste et al., Tetrahedron Lett. 1990,        31, 205];    -   coupling agents based on uronium salts or having a guanidinium        N-oxide structure, for example        N,N,N′,N′-tetramethyl-O-(1H-benzotriazol-1-yl)uronium        hexafluorophosphate [R. Knorr, A. Trzeciak, W. Bannwarth, D.        Gillessen, Tetrahedron Lett. 1989, 30, 1927],        N,N,N,N′-tetramethyl-O-(benzotriazol-1-yl)uronium        tetrafluoroborate, (benzotriazol-1-yloxy)dipiperidinocarbenium        hexafluorophosphate [S. Chen, J. Xu, Tetrahedron Lett. 1992, 33,        647];    -   coupling agents which form acid chlorides, for example        bis-(2-oxo-oxazolidinyl)phosphinic chloride [J. Diago-Mesequer,        Synthesis 1980, 547].

Compounds Ia where X¹ is O, X₃ is a lone pair and R¹ is different fromhydrogen can also be prepared by alkylating the corresponding amides asshown in Scheme 3 (in which R¹ is hydrogen and which can be obtainedaccording to scheme 1 or 2) using suitable alkylating agents in thepresence of bases.

The oxazole or thiazole or imidazole or isoxazole or isothiazolecarboxylic acids IV and their activated derivatives IIa as well as3-aminopyridine compound III are known in the art or are commerciallyavailable or can be prepared by methods known from the literature.

Compounds of the formula I, wherein X¹ is different from oxygen, can beprepared from the compounds Ia by standard methods:

Compounds of the formula I, wherein X¹ is S, can be prepared e.g. byreacting a compound 1a with2,4-bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane-2,4-disulfide orphosphorus pentasulfide according to the method described by M.Jesberger et al. in Synthesis 2003, 1929.

Compounds of the formula I, wherein X¹ is NR^(1a), can be prepared e.g.by reacting a compound Ia with by reacting a compound Ia with2,4-bis(4-methoxyphenyl)-1,3,2,4-dithiadiphosphetane-2,4-disulfide toobtain the corresponding thioamide (compound I, wherein X¹ is S) whichis then reacted with an appropriate amine according to the methoddescribed by V. Glushkov et al. in Pharmaceutical Chemistry Journal2005, 39(10), 533-536.

Compounds of the formula II, wherein X²═SR^(2a), can be prepared byalkylation of the corresponding thioamide (compound I, wherein X¹ is S)by reaction with an alkylating agent according to the method describedby V. Glushkov et al. in Pharmaceutical Chemistry Journal 2005, 39(10),533-536. In a similar manner, compounds I, wherein X² is OR^(2a) orNR^(2b)R^(2c) can be obtained. Compounds of the formula II, whereinX²═SOR^(2a) or SO₂R^(2a) can be obtained by oxidation of compounds IIwith X²═SR^(2a).

Compounds of the formulae I and II, wherein X³ is O, can be prepared byoxidation of compounds I, wherein X³ is a lone pair, according tostandard methods of preparing pyridine N-oxides, e.g. by the methoddescribed C. Botteghi et al. in Journal of Organometallic Chemistry1989, 370, 17-31.

As a rule, the compounds of the formulae I or II can be prepared by themethods described above. If individual compounds cannot be prepared viathe above-described routes, they can be prepared by derivatization ofother compounds I or II or by customary modifications of the synthesisroutes described. For example, in individual cases, certain compounds Ior II can advantageously be prepared from other compounds I or II byester hydrolysis, amidation, esterification, ether cleavage,olefination, reduction, oxidation and the like.

The reaction mixtures are worked up in the customary manner, for exampleby mixing with water, separating the phases, and, if appropriate,purifying the crude products by chromatography, for example on aluminaor on silica gel. Some of the intermediates and end products may beobtained in the form of colorless or pale brown viscous oils which arefreed or purified from volatile components under reduced pressure and atmoderately elevated temperature. If the intermediates and end productsare obtained as solids, they may be purified by recrystallization ortrituration. Ronan please check all the preparation part.

Accordingly, the present invention also provides a method forcontrolling invertebrate pests which method comprises treating thepests, their food supply, their habitat or their breeding ground or acultivated plant, plant propagation materials (such as seed), soil,area, material or environment in which the pests are growing or maygrow, or the materials, cultivated plants, plant propagation materials(such as seed), soils, surfaces or spaces to be protected from pestattack or infestation with a pesticidally effective amount of a compoundof formulae (I) or (II) or a salt or N-oxide thereof or a composition asdefined above.

Preferably, the method of the invention serves for protecting plantpropagation material (such as seed) and the plant which grows therefromfrom invertebrate pest attack or infestation and comprises treating theplant propagation material (such as seed) with a pesticidally effectiveamount of a compound of formulae (I) or (II) or an agriculturallyacceptable salt or N-oxide thereof as defined above or with apesticidally effective amount of an agricultural composition as definedabove and below. The method of the invention is not limited to theprotection of the “substrate” (plant, plant propagation materials, soilmaterial etc.) which has been treated according to the invention, butalso has a preventive effect, thus, for example, according protection toa plant which grows from a treated plant propagation materials (such asseed), the plant itself not having been treated.

In the sense of the present invention, “invertebrate pests” arepreferably selected from arthropods and nematodes, more preferably fromharmful insects, arachnids and nematodes, and even more preferably frominsects, acarids and nematodes. In the sense of the present invention,“invertebrate pests” are most preferably insects.

The invention further provides an agricultural composition for combatingsuch invertebrate pests, which comprises such an amount of at least onecompound of the general formulae I or II or at least one agriculturallyuseful salt or N-oxide thereof and at least one inert liquid and/orsolid agronomically acceptable carrier that has a pesticidal action and,if desired, at least one surfactant.

Such a composition may contain a single active compound of the formulaeI or II or a salt or N-oxide thereof or a mixture of several activecompounds I or II or their salts according to the present invention. Thecomposition according to the present invention may comprise anindividual isomer or mixtures of isomers as well as individual tautomersor mixtures of tautomers.

The compounds of the formulae I or II and the pestidicidal compositionscomprising them are effective agents for controlling arthropod pests andnematodes. Invertebrate pests controlled by the compounds of formulae Ior II include for example

insects from the order of the lepidopterans (Lepidoptera), for exampleAgrotis ypsilon, Agrotis segetum, Alabama argillacea, Anticarsiagemmatalis, Argyresthia conjugella, Autographa gamma, Bupalus piniarius,Cacoecia murinana, Capua reticulana, Chematobia brumata, Choristoneurafumiferana, Choristoneura occidentalis, Cirphis unipuncta, Cydiapomonella, Dendrolimus pini, Diaphania nitidalis, Diatraea grandiosella,Earias insulana, Elasmopalpus lignosellus, Eupoecilia ambiguella,Evetria bouliana, Feltia subterranea, Galleria mellonella, Grapholithafunebrana, Grapholitha molesta, Heliothis armigera, Heliothis virescens,Heliothis zea, Hellula undalis, Hibernia defoliaria, Hyphantria cunea,Hyponomeuta malinellus, Keiferia lycopersicella, Lambdina fiscellaria,Laphygma exigua, Leucoptera coffeella, Leucoptera scitella,Lithocolletis blancardella, Lobesia botrana, Loxostege sticticalis,Lymantria dispar, Lymantria monacha, Lyonetia clerkella, Malacosomaneustria, Mamestra brassicae, Orgyia pseudotsugata, Ostrinia nubilalis,Panolis flammea, Pectinophora gossypiella, Peridroma saucia, Phalerabucephala, Phthorimaea operculella, Phyllocnistis citrella, Pierisbrassicae, Plathypena scabra, Plutella xylostella, Pseudoplusiaincludens, Rhyacionia frustrana, Scrobipalpula absoluta, Sitotrogacerealella, Sparganothis pilleriana, Spodoptera frugiperda, Spodopteralittoralis, Spodoptera litura, Thaumatopoea pityocampa, Tortrixviridana, Trichoplusiani and Zeiraphera canadensis;beetles (Coleoptera), for example Agrilus sinuatus, Agriotes lineatus,Agriotes obscurus, Amphimallus solstitialis, Anisandrus dispar,Anthonomus grandis, Anthonomus pomorum, Atomaria linearis, Blastophaguspiniperda, Blitophaga undata, Bruchus rufimanus, Bruchus pisorum,Bruchus lentis, Byctiscus betulae, Cassida nebulosa, Cerotomatrifurcata, Ceuthorrhynchus assimilis, Ceuthorrhynchus napi, Chaetocnematibialis, Conoderus vespertinus, Crioceris asparagi, Diabroticalongicornis, Diabrotica 12 punctata, Diabrotica virgifera, Epilachnavarivestis, Epitrix hirtipennis, Eutinobothrus brasiliensis, Hylobiusabietis, Hypera brunneipennis, Hypera postica, Ips typographus, Lemabilineata, Lema melanopus, Leptinotarsa decemlineata, Limoniuscalifornicus, Lissorhoptrus oryzophilus, Melanotus communis, Meligethesaeneus, Melolontha hippocastani, Melolontha melolontha, Oulema oryzae,Ortiorrhynchus sulcatus, Otiorrhynchus ovatus, Phaedon cochleariae,Phyllotreta chrysocephala, Phyllophaga sp., Phyllopertha horticola,Phyllotreta nemorum, Phyllotreta striolata, Popillia japonica, Sitonalineatus and Sitophilus granaria;dipterans (Diptera), for example Aedes aegypti, Aedes vexans, Anastrephaludens, Anopheles maculipennis, Ceratitis capitata, Chrysomya bezziana,Chrysornya hominivorax, Chrysomya macellaria, Contarinia sorghicola,Cordylobia anthropophaga, Culex pipiens, Dacus cucurbitae, Dacus oleae,Dasineura brassicae, Fannia canicularis, Gasterophilus intestinalis,Glossina morsitans, Haematobia irritans, Haplodiplosis equestris,Hylernyia platura, Hypoderma lineata, Liriornyza sativae, Liriomyzatrifolii, Lucilia caprina, Lucilia cuprina, Lucilia sericata, Lycoriapectoralis, Mayetiola destructor, Musca domestica, Muscina stabulans,Oestrus ovis, Oscinella frit, Pegomya hysocyami, Phorbia antiqua,Phorbia brassicae, Phorbia coarctata, Rhagoletis cerasi, Rhagoletispomonella, Tabanus bovinus, Tipula oleracea and Tipula paludosa;thrips (Thysanoptera), e.g. Dichromothrips corbetti, Frankliniellafusca, Frankliniella occidentalis, Frankliniella tritici, Scirtothripscitri, Thrips oryzae, Thrips palmi and Thrips tabaci;hymenopterans (Hymenoptera), e.g. Athalia rosae, Atta cephalotes, Attasexdens, Atta texana, Hoplocampa minuta, Hoplocarnpa testudinea,Monomorium pharaonis, Solenopsis gerninata and Solenopsis invicta;heteropterans (Heteroptera), e.g. Acrosternum hilare, Blissusleucopterus, Cyrtopeltis notatus, Dysdercus cingulatus, Dysdercusintermedius, Eurygaster integriceps, Euschistus impictiventris,Leptoglossus phyllopus, Lygus lineolaris, Lygus pratensis, Nezaraviridula, Piesma quadrata, Solubea insularis and Thyanta perditor;homopterans (Homoptera), e.g. Acyrthosiphon onobrychis, Adelges laricis,Aphidula nasturtii, Aphis fabae, Aphis forbesi, Aphis pomi, Aphisgossypii, Aphis grossulariae, Aphis schneideri, Aphis spiraecola, Aphissambuci, Acyrthosiphon pisum, Aulacorthum solani, Bemisia argentifolii,Bemisia tabaci, Brachycaudus cardui, Brachycaudus helichrysi,Brachycaudus persicae, Brachycaudus prunicola, Brevicoryne brassicae,Capitophorus horni, Cerosipha gossypii, Chaetosiphon fragaefolii,Cryptornyzus ribis, Dreyfusia nordmannianae, Dreyfusia piceae, Dysaphisradicola, Dysaulacorthum pseudosolani, Dysaphis plantaginea, Dysaphispyri, Empoasca fabae, Hyalopterus pruni, Hyperomyzus lactucae,Macrosiphum avenae, Macrosiphum euphorbiae, Macrosiphon rosae, Megouraviciae, Melanaphis pyrarius, Metopolophium dirhodum, Myzodes persicae,Myzus ascatonicus, Myzus cerasi, Myzus persicae, Myzus varians,Nasonovia ribis-nigri, Nilaparvata lugens, Pemphigus bursarius,Perkinsiella saccharicida, Phorodon humuli, Psylla mali, Psylla piri,Rhopalomyzus ascalonicus, Rhopalosiphum maidis, Rhopalosiphum padi,Rhopalosiphum insertum, Sappaphis mala, Sappaphis mali, Schizaphisgraminum, Schizoneura lanuginosa, Sitobion avenae, Sogatella furciferaTrialeurodes vaporariorum, Toxoptera aurantiiand, and Viteus vitifolii;termites (Isoptera), e.g. Calotermes flavicollis, Leucotermes flavipes,Reticulitermes flavipes, Reticulitermes lucifugus and Termes natalensis;orthopterans (Orthoptera), e.g. Acheta domestica, Blatta orientalis,Blattella germanica, Forficula auricularia, Gryllotalpa gryllotalpa,Locusta migratoria, Melanoplus bivittatus, Melanoplus femur-rubrum,Melanoplus mexicanus, Melanoplus sanguinipes, Melanoplus spretus,Nomadacris septemfasciata, Periplaneta americana, Schistocercaamericana, Schistocerca peregrina, Stauronotus maroccanus and Tachycinesasynamorus;arachnoidea, such as arachnids (Acarina), e.g. of the familiesArgasidae, Ixodidae and Sarcoptidae, such as Amblyomma americanum,Amblyomma variegatum, Argas persicus, Boophilus annulatus, Boophilusdecoloratus, Boophilus microplus, Dermacentor silvarum, Hyalommatruncatum, Ixodes ricinus, Ixodes rubicundus, Ornithodorus moubata,Otobius megnini, Dermanyssus gallinae, Psoroptes ovis, Rhipicephalusappendiculatus, Rhipicephalus evertsi, Sarcoptes scabiei, andEriophyidae spp. such as Aculus schlechtendali, Phyllocoptrata oleivoraand Eriophyes sheldoni; Tarsonemidae spp. such as Phytonemus pallidusand Polyphagotarsonemus latus; Tenuipalpidae spp. such as Brevipalpusphoenicis; Tetranychidae spp. such as Tetranychus cinnabarinus,Tetranychus kanzawai, Tetranychus pacificus, Tetranychus telarius andTetranychus urticae, Panonychus ulmi, Panonychus citri, and oligonychuspratensis;siphonatera, e.g. Xenopsylla cheopsis, Ceratophyllus spp.

The compositions and compounds of formulae I or II are useful for thecontrol of nematodes, especially plant parasitic nematodes such as rootknot nematodes, Meloidogyne hapla, Meloidogyne incognita, Meloidogynejavanica, and other Meloidogyne species;

cyst-forming nematodes, Globodera rostochiensis and other Globoderaspecies; Heterodera avenae, Heterodera glycines, Heterodera schachtii,Heterodera trifolii, and other Heterodera species; Seed gall nematodes,Anguina species; Stem and foliar nematodes, Aphelenchoides species;Sting nematodes, Belonolaimus longicaudatus and other Belonolaimusspecies; Pine nematodes, Bursaphelenchus xylophilus and otherBursaphelenchus species; Ring nematodes, Criconema species, Criconemellaspecies, Criconemoides species, Mesocriconema species; Stem and bulbnematodes, Ditylenchus destructor, Ditylenchus dipsaci and otherDitylenchus species; Awl nematodes, Dolichodorus species; Spiralnematodes, Heliocotylenchus multicinctus and other Helicotylenchusspecies; Sheath and sheathoid nematodes, Hemicycliophora species andHemicriconemoides species; Hirshmanniella species; Lance nematodes,Hoploaimus species; false rootknot nematodes, Nacobbus species; Needlenematodes, Longidorus elongatus and other Longidorus species; Pinnematodes, Paratylenchus species; Lesion nematodes, Pratylenchusneglectus, Pratylenchus penetrans, Pratylenchus curvitatus, Pratylenchusgoodeyi and other Pratylenchus species; Burrowing nematodes, Radopholussimilis and other Radopholus species; Reniform nematodes, Rotylenchusrobustus and other Rotylenchus species; Scutellonema species; Stubbyroot nematodes, Trichodorus primitivus and other Trichodorus species,Paratrichodorus species Stunt nematodes, Tylenchorhynchus claytoni,Tylenchorhynchus dubius and other Tylenchorhynchus species; Citrusnematodes, Tylenchulus species; Dagger nematodes, Xiphinema species; andother plant parasitic nematode species.

In a preferred embodiment of the invention the compounds of formulae Ior II are used for controlling insects or arachnids, in particularinsects of the orders Lepidoptera, Coleoptera, Thysanoptera andHomoptera and arachnids of the order Acarina. The compounds of theformulae I or II according to the present invention are particularlyuseful for controlling insects of the order Thysanoptera and Homoptera.

The compounds of formula formulae I or II or the pesticidal compositionscomprising them may be used to protect growing plants and crops fromattack or infestation by invertebrate pests, especially insects,acaridae or arachnids by contacting the plant/crop with a pesticidallyeffective amount of compounds of formulae I or II. The term “crop”refers both to growing and harvested crops.

The compounds of formulae I or II can be converted into the customaryformulations, for example solutions, emulsions, suspensions, dusts,powders, pastes and granules. The use form depends on the particularintended purpose; in each case, it should ensure a fine and evendistribution of the compound according to the invention.

The formulations are prepared in a known manner (see e.g. for reviewU.S. Pat. No. 3,060,084, EP-A 707 445 (for liquid concentrates),Browning, “Agglomeration”, Chemical Engineering, Dec. 4, 1967, 147-48,Perry's Chemical Engineer's Handbook, 4th Ed., McGraw-Hill, New York,1963, pages 8-57 and et seq. WO 91/13546, U.S. Pat. No. 4,172,714, U.S.Pat. No. 4,144,050, U.S. Pat. No. 3,920,442, U.S. Pat. No. 5,180,587,U.S. Pat. No. 5,232,701, U.S. Pat. No. 5,208,030, GB 2,095,558, U.S.Pat. No. 3,299,566, Klingman, Weed Control as a Science, John Wiley andSons, Inc., New York, 1961, Hance et al., Weed Control Handbook, 8thEd., Blackwell Scientific Publications, Oxford, 1989 and Mollet, H.,Grubemann, A., Formulation technology, Wiley VCH Verlag GmbH, Weinheim(Germany), 2001, 2. D. A. Knowles, Chemistry and Technology ofAgrochemical Formulations, Kluwer Academic Publishers, Dordrecht, 1998(ISBN 0-7514-0443-8), for example by extending the active compound withauxiliaries suitable for the formulation of agrochemicals, such assolvents and/or carriers, if desired emulsifiers, surfactants anddispersants, preservatives, anti-foaming agents, anti-freezing agents,for seed treatment formulation also optionally colorants and/or bindersand/or gelling agents.

Examples of suitable solvents are water, aromatic solvents (for exampleSolvesso products, xylene), paraffins (for example mineral oilfractions), alcohols (for example methanol, butanol, pentanol, benzylalcohol), ketones (for example cyclohexanone, gamma-butyrolactone),pyrrolidones (N-methylpyrrolidone [NMP], N-octylpyrrolidone [NOP]),acetates (glycol diacetate), glycols, fatty acid dimethylamides, fattyacids and fatty acid esters. In principle, solvent mixtures may also beused

Suitable emulsifiers are non-ionic and anionic emulsifiers (for examplepolyoxyethylene fatty alcohol ethers, alkylsulfonates andarylsulfonates).

Examples of dispersants are lignin-sulfite waste liquors andmethylcellulose.

Suitable surfactants used are alkali metal, alkaline earth metal andammonium salts of lignosulfonic acid, naphthalenesulfonic acid,phenolsulfonic acid, dibutylnaphthalenesulfonic acid,alkylarylsulfonates, alkyl sulphates, alkylsulfonates, fatty alcoholsulfates, fatty acids and sulphated fatty alcohol glycol ethers,furthermore condensates of sulfonated naphthalene and naphthalenederivatives with formaldehyde, condensates of naphthalene or ofnaphthalenesulfonic acid with phenol and formaldehyde, polyoxyethyleneoctylphenol ether, ethoxylated isooctylphenol, octylphenol, nonylphenol,alkylphenol polyglycol ethers, tributylphenyl polyglycol ether,tristearylphenyl polyglycol ether, alkylaryl polyether alcohols, alcoholand fatty alcohol ethylene oxide condensates, ethoxylated castor oil,polyoxyethylene alkyl ethers, ethoxylated polyoxypropylene, laurylalcohol polyglycol ether acetal, sorbitol esters, lignosulfite wasteliquors and methylcellulose.

Substances which are suitable for the preparation of directly sprayablesolutions, emulsions, pastes or oil dispersions are mineral oilfractions of medium to high boiling point, such as kerosene or dieseloil, furthermore coal tar oils and oils of vegetable or animal origin,aliphatic, cyclic and aromatic hydrocarbons, for example toluene,xylene, paraffin, tetrahydronaphthalene, alkylated naphthalenes or theirderivatives, methanol, ethanol, propanol, butanol, cyclohexanol,cyclohexanone, isophorone, highly polar solvents, for example dimethylsulfoxide, N-methylpyrrolidone or water.

Also anti-freezing agents such as glycerin, ethylene glycol, propyleneglycol and bactericides such as can be added to the formulation.

Suitable antifoaming agents are for example antifoaming agents based onsilicon or magnesium stearate.

A suitable preservative is e.g. dichlorophen.

Seed treatment formulations may additionally comprise binders andoptionally colorants.

Binders can be added to improve the adhesion of the active materials onthe seeds after treatment. Suitable binders are block copolymers EO/POsurfactants but also polyvinylalcohols, polyvinylpyrrolidones,polyacrylates, polymethacrylates, polybutenes, polyisobutylenes,polystyrene, polyethyleneamines, polyethyleneamides, polyethyleneimines(Lupasol®, Polymin®), polyethers, polyurethans, polyvinylacetate, tyloseand copolymers derived from these polymers.

Optionally, also colorants can be included in the formulation. Suitablecolorants or dyes for seed treatment formulations are Rhodamin B, C.I.Pigment Red 112, C.I. Solvent Red 1, pigment blue 15:4, pigment blue15:3, pigment blue 15:2, pigment blue 15:1, pigment blue 80, pigmentyellow 1, pigment yellow 13, pigment red 112, pigment red 48:2, pigmentred 48:1, pigment red 57:1, pigment red 53:1, pigment orange 43, pigmentorange 34, pigment orange 5, pigment green 36, pigment green 7, pigmentwhite 6, pigment brown 25, basic violet 10, basic violet 49, acid red51, acid red 52, acid red 14, acid blue 9, acid yellow 23, basic red 10,basic red 108.

An example of a gelling agent is carrageen (Satiagel®).

Powders, materials for spreading and dustable products can be preparedby mixing or concomitantly grinding the active substances with a solidcarrier.

Granules, for example coated granules, impregnated granules andhomogeneous granules, can be prepared by binding the active compounds tosolid carriers.

Examples of solid carriers are mineral earths such as silica gels,silicates, talc, kaolin, attaclay, limestone, lime, chalk, bole, loess,clay, dolomite, diatomaceous earth, calcium sulfate, magnesium sulfate,magnesium oxide, ground synthetic materials, fertilizers, such as, forexample, ammonium sulfate, ammonium phosphate, ammonium nitrate, ureas,and products of vegetable origin, such as cereal meal, tree bark meal,wood meal and nutshell meal, cellulose powders and other solid carriers.

In general, the formulations comprise from 0.01 to 95 by weight,preferably from 0.1 to 90 by weight, of the active compound(s). In thiscase, the active compound(s) are employed in a purity of from 90 to 100by weight, preferably 95 to 100 by weight (according to NMR spectrum).

For seed treatment purposes, respective formulations can be diluted 2-to 10-fold leading to concentrations in the ready to use preparations of0.01 to 60 by weight active compound by weight, preferably 0.1 to 40 byweight.

The compounds of formulae I or II can be used as such, in the form oftheir formulations or the use forms prepared therefrom, for example inthe form of directly sprayable solutions, powders, suspensions ordispersions, emulsions, oil dispersions, pastes, dustable products,materials for spreading, or granules, by means of spraying, atomizing,dusting, spreading or pouring. The use forms depend entirely on theintended purposes; they are intended to ensure in each case the finestpossible distribution of the active compound(s) according to theinvention.

Aqueous use forms can be prepared from emulsion concentrates, pastes orwettable powders (sprayable powders, oil dispersions) by adding water.To prepare emulsions, pastes or oil dispersions, the substances, as suchor dissolved in an oil or solvent, can be homogenized in water by meansof a wetting agent, tackifier, dispersant or emulsifier. However, it isalso possible to prepare concentrates composed of active substance,wetting agent, tackifier, dispersant or emulsifier and if appropriate,solvent or oil, and such concentrates are suitable for dilution withwater.

The active compound concentrations in the ready-to-use preparations canbe varied within relatively wide ranges. In general, they are from0.0001 to 10, preferably from 0.01 to 1 per weight.

The active compound(s) may also be used successfully in theultra-low-volume process (ULV), it being possible to apply formulationscomprising over 95 by weight of active compound, or even to apply theactive compound without additives.

The following are examples of formulations:

1. Products for dilution with water for foliar applications. For seedtreatment purposes, such products may be applied to the seed diluted orundiluted.

A) Water-Soluble Concentrates (SL, LS)

10 parts by weight of the active compound(s) are dissolved in 90 partsby weight of water or a water-soluble solvent. As an alternative,wetting agents or other auxiliaries are added. The active compound(s)dissolves upon dilution with water, whereby a formulation with 10 (w/w)of active compound(s) is obtained.

B) Dispersible Concentrates (DC)

20 parts by weight of the active compound(s) are dissolved in 70 partsby weight of cyclohexanone with addition of 10 parts by weight of adispersant, for example polyvinylpyrrolidone. Dilution with water givesa dispersion, whereby a formulation with 20 (w/w) of active compound(s)is obtained.

C) Emulsifiable Concentrates (EC)

15 parts by weight of the active compound(s) are dissolved in 7 parts byweight of xylene with addition of calcium dodecylbenzenesulfonate andcastor oil ethoxylate (in each case 5 parts by weight). Dilution withwater gives an emulsion, whereby a formulation with 15 (w/w) of activecompound(s) is obtained.

D) Emulsions (EW, EO, ES)

25 parts by weight of the active compound(s) are dissolved in 35 partsby weight of xylene with addition of calcium dodecylbenzenesulfonate andcastor oil ethoxylate (in each case 5 parts by weight). This mixture isintroduced into 30 parts by weight of water by means of an emulsifiermachine (e.g. Ultraturrax) and made into a homogeneous emulsion.Dilution with water gives an emulsion, whereby a formulation with 25(w/w) of active compound(s) is obtained.

E) Suspensions (SC, OD, FS)

In an agitated ball mill, 20 parts by weight of the active compound(s)are comminuted with addition of 10 parts by weight of dispersants,wetting agents and 70 parts by weight of water or of an organic solventto give a fine active compound(s) suspension. Dilution with water givesa stable suspension of the active compound(s), whereby a formulationwith 20 (w/w) of active compound(s) is obtained.

F) Water-Dispersible Granules and Water-Soluble Granules (WG, SG)

50 parts by weight of the active compound(s) are ground finely withaddition of 50 parts by weight of dispersants and wetting agents andmade as water-dispersible or water-soluble granules by means oftechnical appliances (for example extrusion, spray tower, fluidizedbed). Dilution with water gives a stable dispersion or solution of theactive compound(s), whereby a formulation with 50 (w/w) of activecompound(s) is obtained.

G) Water-Dispersible Powders and Water-Soluble Powders (WP, SP, SS, WS)

75 parts by weight of the active compound(s) are ground in arotor-stator mill with addition of 25 parts by weight of dispersants,wetting agents and silica gel. Dilution with water gives a stabledispersion or solution of the active compound(s), whereby a formulationwith 75 (w/w) of active compound(s) is obtained.

H) Gel-Formulation (GF)

In an agitated ball mill, 20 parts by weight of the active compound(s)are comminuted with addition of 10 parts by weight of dispersants, 1part by weight of a gelling agent wetting agents and 70 parts by weightof water or of an organic solvent to give a fine active compound(s)suspension. Dilution with water gives a stable suspension of the activecompound(s), whereby a formulation with 20 (w/w) of active compound(s)is obtained.

2. Products to be applied undiluted for foliar applications. For seedtreatment purposes, such products may be applied to the seed diluted orundiluted.

I) Dustable Powders (DP, DS)

5 parts by weight of the active compound(s) are ground finely and mixedintimately with 95 parts by weight of finely divided kaolin. This givesa dustable product having 5 (w/w) of active compound(s)

J) Granules (GR, FG, GG, MG)

0.5 parts by weight of the active compound(s) is ground finely andassociated with 95.5 parts by weight of carriers, whereby a formulationwith 0.5 (w/w) of active compound(s) is obtained. Current methods areextrusion, spray-drying or the fluidized bed. This gives granules to beapplied undiluted for foliar use

K) ULV Solutions (UL)

10 parts by weight of the active compound(s) are dissolved in 90 partsby weight of an organic solvent, for example xylene. This gives aproduct having 10 (w/w) of active compound(s), which is appliedundiluted for foliar use.

The compounds of formulae I or II are also suitable for the treatment ofplant propagation materials (such as seed). Conventional seed treatmentformulations include for example flowable concentrates FS, solutions LS,powders for dry treatment DS, water dispersible powders for slurrytreatment WS, water-soluble powders SS and emulsion ES and EC and gelformulation GF. These formulations can be applied to the seed diluted orundiluted. Application to the seeds is carried out before sowing, eitherdirectly on the seeds or after having pre-germinated the latter

In a preferred embodiment a FS formulation is used for seed treatment.Typically, a FS formulation may comprise 1 to 800 g/l of activeingredient, 1 to 200 g/l Surfactant, 0 to 200 g/l antifreezing agent, 0to 400 g/l of binder, 0 to 200 g/l of a pigment and up to 1 liter of asolvent, preferably water.

Other preferred FS formulations of compounds of formulae I or II forseed treatment comprise from 0.5 to 80 wt of the active ingredient, from0.05 to 5 wt of a wetting agent, from 0.5 to 15 wt of a dispersingagent, from 0.1 to 5 wt of a thickener, from 5 to 20 wt of ananti-freeze agent, from 0.1 to 2 wt of an anti-foam agent, from 1 to 20wt of a pigment and/or a dye, from 0 to 15 wt of a sticker/adhesionagent, from 0 to 75 wt of a filler/vehicle, and from 0.01 to 1 wt of apreservative.

Various types of oils, wetting agents, adjuvants, herbicides,fungicides, other pesticides, or bactericides may be added to the activeingredients, if appropriate just immediately prior to use (tank mix).These agents usually are admixed with the agents according to theinvention in a weight ratio of 1:10 to 10:1.

The compounds of formulae I or II are effective through both contact(via soil, glass, wall, bed net, carpet, plant parts or animal parts),and ingestion (bait, or plant part).

For use against ants, termites, wasps, flies, mosquitoes, crickets, orcockroaches, compounds of formulae I or II are preferably used in a baitcomposition.

The bait can be a liquid, a solid or a semisolid preparation (e.g. agel). Solid baits can be formed into various shapes and forms suitableto the respective application e.g. granules, blocks, sticks, disks.Liquid baits can be filled into various devices to ensure properapplication, e.g. open containers, spraying devices, droplet sources, orevaporation sources. Gels can be based on aqueous or oily matrices andcan be formulated to particular necessities in terms of stickiness,moisture retention or aging characteristics.

The bait employed in the composition is a product, which is sufficientlyattractive to incite insects such as ants, termites, wasps, flies,mosquitoes, crickets etc. or cockroaches to eat it. The attractivenesscan be manipulated by using feeding stimulants or sex pheromones. Foodstimulants are chosen, for example, but not exclusively, from animaland/or plant proteins (meat-, fish- or blood meal, insect parts, eggyolk), from fats and oils of animal and/or plant origin, or mono-,oligo- or polyorganosaccharides, especially from sucrose, lactose,fructose, dextrose, glucose, starch, pectin or even molasses or honey.Fresh or decaying parts of fruits, crops, plants, animals, insects orspecific parts thereof can also serve as a feeding stimulant. Sexpheromones are known to be more insect specific. Specific pheromones aredescribed in the literature and are known to those skilled in the art.

Formulations of compounds of formulae I or II as aerosols (e.g. in spraycans), oil sprays or pump sprays are highly suitable for thenon-professional user for controlling pests such as flies, fleas, ticks,mosquitos or cockroaches. Aerosol recipes are preferably composed of theactive compound, solvents such as lower alcohols (e.g. methanol,ethanol, propanol, butanol), ketones (e.g. acetone, methyl ethylketone), paraffin hydrocarbons (e.g. kerosenes) having boiling ranges ofapproximately 50 to 250° C., dimethyl-formamide, N-methylpyrrolidone,dimethyl sulphoxide, aromatic hydrocarbons such as toluene, xylene,water, furthermore auxiliaries such as emulsifiers such as sorbitolmonooleate, oleyl ethoxylate having 3 to 7 mol of ethylene oxide, fattyalcohol ethoxylate, perfume oils such as ethereal oils, esters of mediumfatty acids with lower alcohols, aromatic carbonyl compounds, ifappropriate stabilizers such as sodium benzoate, am-photericsurfactants, lower epoxides, triethyl orthoformate and, if required,propellants such as propane, butane, nitrogen, compressed air, dimethylether, carbon dioxide, nitrous oxide, or mixtures of these gases.

The oil spray formulations differ from the aerosol recipes in that nopropellants are used.

The compounds of formulae I or II and their respective compositions canalso be used in mosquito and fumigating coils, smoke cartridges,vaporizer plates or long-term vaporizers and also in moth papers, mothpads or other heat-independent vaporizer systems.

Methods to control infectious diseases transmitted by insects (e.g.malaria, dengue and yellow fever, lymphatic filariasis, andleishmaniasis) with compounds of formulae I or II and its respectivecompositions also comprise treating surfaces of huts and houses, airspraying and impregnation of curtains, tents, clothing items, bed nets,tsetse-fly trap or the like. Insecticidal compositions for applicationto fibers, fabric, knitgoods, non-wovens, netting material or foils andtarpaulins preferably comprise a mixture including the insecticide,optionally a repellent and at least one binder. Suitable repellents forexample are N,N-diethyl-meta-toluamide (DEET),N,N-diethylphenylacetamide (DEPA),1-(3-cyclohexan-1-yl-carbonyl)-2-methylpiperine,(2-hydroxymethylcyclohexyl)acetic acid lactone, 2-ethyl-1,3-hexandiol,indalone, Methylneodecanamide (MNDA), a pyrethroid not used for insectcontrol such as{(+/−)-3-allyl-2-methyl-4-oxocyclopent-2-(+)-enyl-(+)-trans-chrysantemate(Esbiothrin), a repellent derived from or identical with plant extractslike limonene, eugenol, (+)-Eucamalol (1), (−)-1-epi-eucamalol or crudeplant extracts from plants like Eucalyptus maculata, Vitex rotundifolia,Cymbopogan martinii, Cymbopogan citratus (lemon grass), Cymopogannartdus (citronella). Suitable binders are selected for example frompolymers and copolymers of vinyl esters of aliphatic acids (such as suchas vinyl acetate and vinyl versatate), acrylic and methacrylic esters ofalcohols, such as butyl acrylate, 2-ethylhexylacrylate, and methylacrylate, mono- and diethylenically unsaturated hydrocarbons, such asstyrene, and aliphatic diens, such as butadiene.

The impregnation of curtains and bednets is done in general by dippingthe textile material into emulsions or dispersions of the activecompounds of formulae I and II or spraying them onto the nets.

Methods which can be employed for treating the seed are, in principle,all suitable seed treatment and especially seed dressing techniquesknown in the art, such as seed coating (e.g. seed pelleting), seeddusting and seed imbibition (e.g. seed soaking). Here, “seed treatment”refers to all methods that bring seeds and the compounds of formulae Ior II into contact with each other, and “seed dressing” to methods ofseed treatment which provide the seeds with an amount of the compoundsof formulae I or II, i.e. which generate a seed comprising the compoundof formulae I or II. In principle, the treatment can be applied to theseed at any time from the harvest of the seed to the sowing of the seed.The seed can be treated immediately before, or during, the planting ofthe seed, for example using the “planter's box” method. However, thetreatment may also be carried out several weeks or months, for exampleup to 12 months, before planting the seed, for example in the form of aseed dressing treatment, without a substantially reduced efficacy beingobserved.

Expediently, the treatment is applied to unsown seed. As used herein,the term “unsown seed” is meant to include seed at any period from theharvest of the seed to the sowing of the seed in the ground for thepurpose of germination and growth of the plant.

Specifically, a procedure is followed in the treatment in which the seedis mixed, in a suitable device, for example a mixing device for solid orsolid/liquid mixing partners, with the desired amount of seed treatmentformulations, either as such or after previous dilution with water,until the composition is distributed uniformly on the seed. Ifappropriate, this is followed by a drying step.

The compounds of formulae I or II or the enantiomers or veterinarilyacceptable salts thereof are in particular also suitable for being usedfor combating parasites in and on animals.

A further object of the present invention is therefore to provide newmethods for controlling parasites in and on animals. Another object ofthe invention is to provide safer pesticides for animals. Another objectof the invention is further to provide pesticides for animals that maybe used in lower doses than existing pesticides. And another object ofthe invention is to provide pesticides for animals, which provide a longresidual control of the parasites.

The invention also relates to compositions containing a parasiticidallyeffective amount of compounds of formulae I or II or the enantiomers orveterinarily acceptable salts thereof and an acceptable carrier, forcombating parasites in and on animals.

The present invention also provides a method for treating, controlling,preventing and protecting animals against infestation and infection byparasites, which comprises orally, topically or parenterallyadministering or applying to the animals a parasiticidally effectiveamount of compounds of formulae I or II or the enantiomers orveterinarily acceptable salts thereof and an acceptable carrier or acomposition comprising it.

The present invention also provides a non-therapeutic method fortreating, controlling, preventing and protecting animals againstinfestation and infection by parasites, which comprises applying to alocus-P a parasiticidally effective amount of a compound of formulae Ior II or the enantiomers or veterinarily acceptable salts thereof and anacceptable carrier or a composition comprising it.

The invention also provides a process for the preparation of acomposition for treating, controlling, preventing or protecting animalsagainst infestation or infection by parasites which comprises includinga parasiticidally effective amount of a compound of formulae I or II orthe enantiomers or veterinarily acceptable salts thereof and anacceptable carrier or a composition comprising it.

The invention relates further to the use of compounds of formula I fortreating, controlling, preventing or protecting animals againstinfestation or infection by parasites. The invention relates also to theuse of a compound of formulae I or II or the enantiomers or veterinarilyacceptable salts thereof and an acceptable carrier or a compositioncomprising it for the manufacture of a medicament for the therapeutictreatment of animals against infections or infestions by parasites.

Activity of compounds against agricultural pests does not suggest theirsuitability for control of endo- and ectoparasites in and on animalswhich requires, for example, low, nonemetic dosages in the case of oralapplication, metabolic compatibility with the animal, low toxicity, anda safe handling.

Surprisingly, it has been found that compounds of formulae I or II aresuitable for combating endo- and ectoparasites in and on animals.

Compounds of formulae I or II or the enantiomers or veterinarilyacceptable salts thereof and compositions comprising them are preferablyused for controlling and preventing infestations and infections animalsincluding, warm-blooded animals (including humans) and fish. They arefor example suitable for controlling and preventing infestations andinfections in mammals such as cattle, sheep, swine, camels, deer,horses, pigs, poultry, rabbits, goats, dogs and cats, water buffalo,donkeys, fallow deer and reindeer, and also in fur-bearing animals suchas mink, chinchilla and raccoon, birds such as hens, geese, turkeys andducks and fish such as fresh- and salt-water fish such as trout, carpand eels.

Compounds of formulae I or II or the enantiomers or veterinarilyacceptable salts thereof and compositions comprising them are preferablyused for controlling and preventing infestations and infections indomestic animals, such as dogs or cats.

Infestations in warm-blooded animals and fish include, but are notlimited to, lice, biting lice, ticks, nasal bots, keds, biting flies,muscoid flies, flies, myiasitic fly larvae, chiggers, gnats, mosquitoesand fleas.

The compounds of formulae I or II or the enantiomers or veterinarilyacceptable salts thereof and compositions comprising them are suitablefor systemic and/or non-systemic control of ecto- and/or endoparasites.They are active against all or some stages of development.

The compounds of formulae I or II are especially useful for combatingectoparasites.

The compounds of formulae I or II are especially useful for combatingparasites of the following orders and species, respectively:

fleas (Siphonaptera), e.g. Ctenocephalides felis, Ctenocephalides canis,Xenopsylla cheopis, Pulex irritans, Tunga penetrans, and Nosopsyllusfasciatus,

cockroaches (Blattaria-Blattodea), e.g. Blattella germanica, Blattellaasahinae, Periplaneta americana, Periplaneta japonica, Periplanetabrunnea, Periplaneta fuligginosa, Periplaneta australasiae, and Blattaorientalis,

flies, mosquitoes (Diptera), e.g. Aedes aegypti, Aedes albopictus, Aedesvexans, Anastrepha ludens, Anopheles maculipennis, Anopheles crucians,Anopheles albimanus, Anopheles gambiae, Anopheles freeborni, Anophelesleucosphyrus, Anopheles minimus, Anopheles quadrimaculatus, Calliphoravicina, Chrysornya bezziana, Chrysomya hominivorax, Chrysomyamacellaria, Chrysops discalis, Chrysops silacea, Chrysops atlanticus,Cochliomyia hominivorax, Cordylobia anthropophaga, Culicoides furens,Culex pipiens, Culex nigripalpus, Culex quinquefasciatus, Culextarsalis, Culiseta inornata, Culiseta melanura, Dermatobia hominis,Fannia canicularis, Gasterophilus intestinalis, Glossina morsitans,Glossina palpalis, Glossina fuscipes, Glossina tachinoides, Haematobiairritans, Haplodiplosis equestris, Hippelates spp., Hypoderma lineata,Leptoconops torrens, Lucilia caprina, Lucilia cuprina, Lucilia sericata,Lycoria pectoralis, Mansonia spp., Musca domestica, Muscina stabulans,Oestrus ovis, Phlebotomus argentipes, Psorophora columbiae, Psorophoradiscolor, Prosimulium mixtum, Sarcophaga haemorrhoidalis, Sarcophagasp., Simulium vittatum, Stomoxys calcitrans, Tabanus bovinus, Tabanusatratus, Tabanus lineola, and Tabanus similis,lice (Phthiraptera), e.g. Pediculus humanus capitis, Pediculus humanuscorporis, Pthirus pubis, Haematopinus eurysternus, Haematopinus suis,Linognathus vituli, Bovicola bovis, Menopon gallinae, Menacanthusstramineus and Solenopotes capillatus,ticks and parasitic mites (Parasitiformes): ticks (Ixodida), e.g. Ixodesscapularis, Ixodes holocyclus, Ixodes pacificus, Rhiphicephalussanguineus, Dermacentor andersoni, Dermacentor variabilis, Amblyommaamericanum, Ambryomma maculatum, Ornithodorus hermsi, Ornithodorusturicata and parasitic mites (Mesostigmata), e.g. Ornithonyssus bacotiand Dermanyssus gallinae,actinedida (Prostigmata) and Acaridida (Astigmata) e.g. Acarapis spp.,Cheyletiella spp., Ornithocheyletia spp., Myobia spp., Psorergates spp.,Demodex spp., Trombicula spp., Listrophorus spp., Acarus spp.,Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus spp.,Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes spp.,Notoedres spp., Knemidocoptes spp., Cytodites spp., and Laminosioptesspp,bugs (Heteropterida): Cimex lectularius, Cimex hemipterus, Reduviussenilis, Triatoma spp., Rhodnius ssp., Panstrongylus ssp. and Ariluscritatus,Anoplurida, e.g. Haematopinus spp., Linognathus spp., Pediculus spp.,Phtirus spp., and Solenopotes spp,Mallophagida (suborders Arnblycerina and Ischnocerina), e.g. Trimenoponspp., Menopon spp., Trinoton spp., Bovicola spp., Werneckiella spp.,Lepikentron spp., Trichodectes spp., and Felicola spp,Roundworms Nematoda:

Wipeworms and Trichinosis (Trichosyringida), e.g. Trichinellidae(Trichinella spp.), (Trichuridae) Trichuris spp., Capillaria spp,

Rhabditida, e.g. Rhabditis spp, Strongyloides spp., Helicephalobus spp,

Strongylida, e.g. Strongylus spp., Ancylostoma spp., Necator americanus,Bunostomum spp. (Hookworm), Trichostrongylus spp., Haemonchus contortus,Ostertagia spp., Cooperia spp, Nematodirus spp., Dictyocaulus spp.,Cyathostoma spp., Oesophagostomum spp., Stephanurus dentatus, Ollulanusspp., Chabertia spp., Stephanurus dentatus, Syngamus trachea,Ancylostoma spp., Uncinaria spp., Globocephalus spp., Necator spp.,Metastrongylus spp., Muellerius capillaris, Protostrongylus spp.,Angiostrongylus spp., Parelaphostrongylus spp. Aleurostrongylusabstrusus, and Dioctophyma renale,

Intestinal roundworms (Ascaridida), e.g. Ascaris lumbricoides, Ascarissuum, Ascaridia galli, Parascaris equorum, Enterobius vermicularis(Threadworm), Toxocara canis, Toxascaris leonine, Skrjabinema spp., andOxyuris equi,

Camallanida, e.g. Dracunculus medinensis (guinea worm),

Spirurida, e.g. Thelazia spp. Wuchereria spp., Brugia spp., Onchocercaspp., Dirofilari spp.a, Dipetalonema spp., Setaria spp., Elaeophoraspp., Spirocerca lupi, and Habronema spp.,

Thorny headed worms (Acanthocephala), e.g. Acanthocephalus spp.,Macracanthorhynchus hirudinaceus and Oncicola spp,

Planarians (Plathelminthes):

Flukes (Trematoda), e.g. Faciola spp., Fascioloides magna, Paragonimusspp., Dicrocoelium Fasciolopsis buski, Clonorchis sinensis, Schistosomaspp., Trichobilharzia spp., Alaria alata, Paragonimus spp., andNanocyetes spp,

Cercomeromorpha, in particular Cestoda (Tapeworms), e.g.Diphyllobothrium spp., Tenia spp., Echinococcus spp., Dipylidiumcaninum, Multiceps spp., Hymenolepis spp., Mesocestoides spp.,Varnpirolepis spp., Moniezia spp., Anoplocephala spp., Sirometra spp.,Anoplocephala spp., and Hymenolepis spp.

The compounds of formulae I or II and compositions containing them areparticularly useful for the control of pests from the orders Diptera,Siphonaptera and Ixodida.

Moreover, the use of the compounds of formulae I or II and compositionscontaining them for combating mosquitoes is especially preferred.

The use of the compounds of formulae I or II and compositions containingthem for combating flies is a further preferred embodiment of thepresent invention.

Furthermore, the use of the compounds of formulae I or II andcompositions containing them for combating fleas is especiallypreferred.

The use of the compounds of formula formulae I or II and compositionscontaining them for combating ticks is a further preferred embodiment ofthe present invention.

The compounds of formulae I or II and compositions containing them alsoare especially useful for combating endoparasites (roundworms nematoda,thorny headed worms and planarians).

The compounds of formulae I or II and compositions containing them canbe effective through both contact (via soil, glass, wall, bed netcarpet, blankets or animal parts) and ingestion (e.g. baits).

The present invention relates to the therapeutic and the non-therapeuticuse of compounds of formulae I or II and compositions containing themfor controlling and/or combating parasites in and/or on animals.

The compounds of formulae I or II and compositions containing them maybe used to protect the animals from attack or infestation by parasitesby contacting them with a parasitically effective amount of compounds offormulae I or II and compositions containing them. As such, “contacting”includes both direct contact (applying the pesticidalmixtures/compositions directly on the parasite, which may include anindirect contact at it's locus-P, and optionally also administrating thepesticidal mixtures/composition directly on the animal) and indirectcontact (applying the compounds/compositions to the locus of theparasite). The contact of the parasite through application to its locusis an example of a non-therapeutic use of compounds of formula I.

“Locus-P” as defined above means the habitat, food supply, breedingground, area, material or environment in which a parasite is growing ormay grow outside of the animal. The compounds of the invention can alsobe applied preventively to places at which occurrence of the pests orparasites is expected.

Administration can be carried out both prophylactically andtherapeutically.

Administration of the active compounds is carried out directly or in theform of suitable preparations, orally, topically/dermally orparenterally.

For oral administration to warm-blooded animals, the compounds offormula I or II may be formulated as animal feeds, animal feed premixes,animal feed concentrates, pills, solutions, pastes, suspensions,drenches, gels, tablets, boluses and capsules. In addition, thecompounds of formulae I or II may be administered to the animals intheir drinking water. For oral administration, the dosage form chosenshould provide the animal with 0.01 mg/kg to 100 mg/kg of animal bodyweight per day of the formulae I or II compound, preferably with 0.5mg/kg to 100 mg/kg of animal body weight per day. Alternatively, thecompounds of formulae I or II may be administered to animalsparenterally, for example, by intraruminal, intramuscular, intravenousor subcutaneous injection. The compounds of formulae I or II may bedispersed or dissolved in a physiologically acceptable carrier forsubcutaneous injection. Alternatively, the compounds of formulae I or IImay be formulated into an implant for subcutaneous administration. Inaddition the compounds of formulae I or II may be transdermallyadministered to animals. For parenteral administration, the dosage formchosen should provide the animal with 0.01 mg/kg to 100 mg/kg of animalbody weight per day of the compounds of formulae I or II.

The compounds of formulae I or II may also be applied topically to theanimals in the form of dips, dusts, powders, collars, medallions,sprays, shampoos, spot-on and pour-on formulations and in ointments oroil-in-water or water-in-oil emulsions. For topical application, dipsand sprays usually contain 0.5 ppm to 5 000 ppm and preferably 1 ppm to3 000 ppm of the compounds of formulae I or II. In addition, thecompounds of formulae I or II may be formulated as ear tags for animals,particularly quadrupeds such as cattle and sheep.

Suitable Preparations are:

Solutions such as oral solutions, concentrates for oral administrationafter dilution, solutions for use on the skin or in body cavities,pouring-on formulations, gels;

Emulsions and suspensions for oral or dermal administration; semi-solidpreparations;

Formulations in which the active compound is processed in an ointmentbase or in an oil-in-water or water-in-oil emulsion base;

Solid preparations such as powders, premixes or concentrates, granules,pellets, tablets, boluses, capsules; aerosols and inhalants, and activecompound-containing shaped articles.

Compositions suitable for injection are prepared by dissolving theactive ingredient in a suitable solvent and optionally adding furtheringredients such as acids, bases, buffer salts, preservatives, andsolubilizers. The solutions are filtered and filled sterile.

Suitable solvents are physiologically tolerable solvents such as water,alkanols such as ethanol, butanol, benzyl alcohol, glycerol, propyleneglycol, polyethylene glycols, N-methylpyrrolidone, 2-pyrrolidone, andmixtures thereof.

The active compounds can optionally be dissolved in physiologicallytolerable vegetable or synthetic oils which are suitable for injection.

Suitable solubilizers are solvents which promote the dissolution of theactive compound in the main solvent or prevent its precipitation.Examples are polyvinylpyrrolidone, polyvinyl alcohol, polyoxyethylatedcastor oil, and polyoxyethylated sorbitan ester.

Suitable preservatives are benzyl alcohol, trichlorobutanol,p-hydroxybenzoic acid esters, and n-butanol.

Oral solutions are administered directly. Concentrates are administeredorally after prior dilution to the use concentration. Oral solutions andconcentrates are prepared according to the state of the art and asdescribed above for injection solutions, sterile procedures not beingnecessary.

Solutions for use on the skin are trickled on, spread on, rubbed in,sprinkled on or sprayed on

Solutions for use on the skin are prepared according to the state of theart and according to what is described above for injection solutions,sterile procedures not being necessary.

Further suitable solvents are polypropylene glycol, phenyl ethanol,phenoxy ethanol, ester such as ethyl or butyl acetate, benzyl benzoate,ethers such as alkyleneglycol alkylether, e.g. dipropylenglycolmonomethylether, ketons such as acetone, methylethylketone, aromatichydrocarbons, vegetable and synthetic oils, dimethylformamide,dimethylacetamide, transcutol, solketal, propylencarbonate, and mixturesthereof.

It may be advantageous to add thickeners during preparation. Suitablethickeners are inorganic thickeners such as bentonites, colloidalsilicic acid, aluminium monostearate, organic thickeners such ascellulose derivatives, polyvinyl alcohols and their copolymers,acrylates and methacrylates.

Gels are applied to or spread on the skin or introduced into bodycavities. Gels are prepared by treating solutions which have beenprepared as described in the case of the injection solutions withsufficient thickener that a clear material having an ointment-likeconsistency results. The thickeners employed are the thickeners givenabove.

Pour-on formulations are poured or sprayed onto limited areas of theskin, the active compound penetrating the skin and acting systemically.

Pour-on formulations are prepared by dissolving, suspending oremulsifying the active compound in suitable skin-compatible solvents orsolvent mixtures. If appropriate, other auxiliaries such as colorants,bioabsorption-promoting substances, antioxidants, light stabilizers,adhesives are added.

Suitable solvents are water, alkanols, glycols, polyethylene glycols,polypropylene glycols, glycerol, aromatic alcohols such as benzylalcohol, phenylethanol, phenoxyethanol, esters such as ethyl acetate,butyl acetate, benzyl benzoate, ethers such as alkylene glycol alkylethers such as dipropylene glycol monomethyl ether, diethylene glycolmono-butyl ether, ketones such as acetone, methyl ethyl ketone, cycliccarbonates such as propylene carbonate, ethylene carbonate, aromaticand/or aliphatic hydrocarbons, vegetable or synthetic oils, DMF,dimethylacetamide, N-alkylpyrrolidones such as N-Methylpyrrolidone,N-butylpyrrolidone or N-octylpyrrolidone, 2-pyrrolidone,2,2-dimethyl-4-oxy-methylene-1,3-dioxolane and glycerol formal.

Suitable colorants are all colorants permitted for use on animals andwhich can be dissolved or suspended.

Suitable absorption-promoting substances are, for example, DMSO,spreading oils such as isopropyl myristate, dipropylene glycolpelargonate, silicone oils and copolymers thereof with polyethers, fattyacid esters, triglycerides, fatty alcohols.

Suitable antioxidants are sulfites or metabisulfites such as potassiummetabisulfite, ascorbic acid, butylhydroxytoluene, butylhydroxyanisole,tocopherol.

Suitable light stabilizers are, for example, novantisolic acid.

Suitable adhesives are for example, cellulose derivatives, starchderivatives, polyacrylates, natural polymers such as alginates, gelatin.

Emulsions can be administered orally, dermally or as injections.

Emulsions are either of the water-in-oil type or of the oil-in-watertype.

They are prepared by dissolving the active compound either in thehydrophobic or in the hydrophilic phase and homogenizing this with thesolvent of the other phase with the aid of suitable emulsifiers and, ifappropriate, other auxiliaries such as colorants, absorption-promotingsubstances, preservatives, antioxidants, light stabilizers,viscosity-enhancing substances.

Suitable Hydrophobic Phases (Oils) are:

liquid paraffins, silicone oils, natural vegetable oils such as sesameoil, almond oil, castor oil, synthetic triglycerides such ascaprylic/capric biglyceride, triglyceride mixture with vegetable fattyacids of the chain length C₈-C₁₂ or other specially selected naturalfatty acids, partial glyceride mixtures of saturated or unsaturatedfatty acids possibly also containing hydroxyl groups, mono- anddiglycerides of the C₈-C₁₀ fatty acids, fatty acid esters such as ethylstearate, di-n-butyryl adipate, hexyl laurate, dipropylene glycolperlargonate, esters of a branched fatty acid of medium chain lengthwith saturated fatty alcohols of chain length C₁₆-C₁₈, isopropylmyristate, isopropyl palmitate, caprylic/capric acid esters of saturatedfatty alcohols of chain length C₁₂-C₁₈, isopropyl stearate, oleyloleate, decyl oleate, ethyl oleate, ethyl lactate, waxy fatty acidesters such as synthetic duck coccygeal gland fat, dibutyl phthalate,diisopropyl adipate, and ester mixtures related to the latter, fattyalcohols such as isotridecyl alcohol, 2-octyldodecanol, cetylstearylalcohol, oleyl alcohol, and fatty acids such as oleic acid and mixturesthereof.

Suitable hydrophilic phases are: water, alcohols such as propyleneglycol, glycerol, sorbitol and mixtures thereof.

Suitable Emulsifiers are:

non-ionic surfactants, e.g. polyethoxylated castor oil, polyethoxylatedsorbitan monooleate, sorbitan monostearate, glycerol monostearate,polyoxyethyl stearate, alkylphenol polyglycol ether; ampholyticsurfactants such as di-sodium N-lauryl-p-iminodipropionate or lecithin;anionic surfactants, such as sodium lauryl sulfate, fatty alcohol ethersulfates, mono/dialkyl polyglycol ether orthophosphoric acid estermonoethanolamine salt; cation-active surfactants, such ascetyltrimethylammonium chloride.

Suitable further auxiliaries are: substances which enhance the viscosityand stabilize the emulsion, such as carboxymethylcellulose,methylcellulose and other cellulose and starch derivatives,polyacrylates, alginates, gelatin, gum arabic, polyvinylpyrrolidone,polyvinyl alcohol, copolymers of methyl vinyl ether and maleicanhydride, polyethylene glycols, waxes, colloidal silicic acid ormixtures of the substances mentioned.

Suspensions can be administered orally or topically/dermally. They areprepared by suspending the active compound in a suspending agent, ifappropriate with addition of other auxiliaries such as wetting agents,colorants, bioabsorption-promoting substances, preservatives,antioxidants, light stabilizers.

Liquid suspending agents are all homogeneous solvents and solventmixtures.

Suitable wetting agents (dispersants) are the emulsifiers given above.

Other auxiliaries which may be mentioned are those given above.

Semi-solid preparations can be administered orally ortopically/dermally. They differ from the suspensions and emulsionsdescribed above only by their higher viscosity. For the production ofsolid preparations, the active compound is mixed with suitableexcipients, if appropriate with addition of auxiliaries, and broughtinto the desired form.

Suitable excipients are all physiologically tolerable solid inertsubstances. Those used are inorganic and organic substances. Inorganicsubstances are, for example, sodium chloride, carbonates such as calciumcarbonate, hydrogencarbonates, aluminium oxides, titanium oxide, silicicacids, argillaceous earths, precipitated or colloidal silica, orphosphates. Organic substances are for example, sugar, cellulose,foodstuffs and feeds such as milk powder, animal meal, grain meals andshreds, starches.

Suitable auxiliaries are preservatives, antioxidants, and/or colorantswhich have been mentioned above.

Other suitable auxiliaries are lubricants and glidants such as magnesiumstearate, stearic acid, talc, bentonites, disintegration-promotingsubstances such as starch or crosslinked polyvinylpyrrolidone, binderssuch as starch, gelatin or linear polyvinylpyrrolidone, and dry binderssuch as microcrystalline cellulose.

In general, “parasiticidally effective amount” means the amount ofactive ingredient needed to achieve an observable effect on growth,including the effects of necrosis, death, retardation, prevention, andremoval, destruction, or otherwise diminishing the occurrence andactivity of the target organism. The parasiticidally effective amountcan vary for the various compounds/compositions used in the invention. Aparasiticidally effective amount of the compositions will also varyaccording to the prevailing conditions such as desired parasiticidaleffect and duration, target species, mode of application, and the like.

The compositions which can be used in the invention can comprisegenerally from about 0.001 to 95 of the compound of formulae I or II.

Generally, it is favorable to apply the compounds of formulae I or II intotal amounts of 0.5 mg/kg to 100 mg/kg per day, preferably 1 mg/kg to50 mg/kg per day.

Ready-to-use preparations contain the compounds acting againstparasites, preferably ectoparasites, in concentrations of 10 ppm to 80percent by weight, preferably from 0.1 to 65 percent by weight, morepreferably from 1 to 50 percent by weight, most preferably from 5 to 40percent by weight.

Preparations which are diluted before use contain the compounds actingagainst ectoparasites in concentrations of 0.5 to 90 percent by weight,preferably of 1 to 50 percent by weight.

Furthermore, the preparations comprise the compounds of formulae I or IIagainst endoparasites in concentrations of 10 ppm to 2 percent byweight, preferably of 0.05 to 0.9 percent by weight, very particularlypreferably of 0.005 to 0.25 percent by weight.

In a preferred embodiment of the present invention, the compositionscomprising the compounds of formulae I or II are applieddermally/topically.

In a further preferred embodiment, the topical application is conductedin the form of compound-containing shaped articles such as collars,medallions, ear tags, bands for fixing at body parts, and adhesivestrips and foils.

Generally, it is favorable to apply solid formulations which releasecompounds of formulae I or II in total amounts of 10 mg/kg to 300 mg/kg,preferably 20 mg/kg to 200 mg/kg, most preferably 25 mg/kg to 160 mg/kgbody weight of the treated animal in the course of three weeks.

For the preparation of the shaped articles, thermoplastic and flexibleplastics as well as elastomers and thermoplastic elastomers are used.Suitable plastics and elastomers are polyvinyl resins, polyurethane,polyacrylate, epoxy resins, cellulose, cellulose derivatives, polyamidesand polyester which are sufficiently compatible with the compounds offormulae I or II. A detailed list of plastics and elastomers as well aspreparation procedures for the shaped articles is given e.g. in WO03/086075.

Compositions to be used according to this invention may also containother active ingredients, for example other pesticides, insecticides,herbicides, fungicides, other pesticides, or bactericides, fertilizerssuch as ammonium nitrate, urea, potash, and super-phosphate,phytotoxicants and plant growth regulators, safeners and nematicides.These additional ingredients may be used sequentially or in combinationwith the above-described compositions, if appropriate also added onlyimmediately prior to use (tank mix). For example, the plant(s) may besprayed with a composition of this invention either before or afterbeing treated with other active ingredients.

These agents can be admixed with the agents used according to theinvention in a weight ratio of 1:10 to 10:1. Mixing the compounds offormulae I or II or the compositions comprising them in the use form aspesticides with other pesticides frequently results in a broaderpesticidal spectrum of action.

The following list M of pesticides together with which the compoundsaccording to the invention can be used and with which potentialsynergistic effects might be produced, is intended to illustrate thepossible combinations, but not to impose any limitation:

M.1. Organo(thio)phosphate compounds: acephate, azamethiphos,azinphos-ethyl, azinphos-methyl, chlorethoxyfos, chlorfenvinphos,chlormephos, chlorpyrifos, chlorpyrifos-methyl, coumaphos, cyanophos,demeton-S-methyl, diazinon, dichlorvos/DDVP, dicrotophos, dimethoate,dimethylvinphos, disulfoton, EPN, ethion, ethoprophos, famphur,fenamiphos, fenitrothion, fenthion, flupyrazophos, fosthiazate,heptenophos, isoxathion, malathion, mecarbam, methamidophos,methidathion, mevinphos, monocrotophos, naled, omethoate,oxydemeton-methyl, parathion, parathion-methyl, phenthoate, phorate,phosalone, phosmet, phosphamidon, phoxim, pirimiphos-methyl, profenofos,propetamphos, prothiofos, pyraclofos, pyridaphenthion, quinalphos,sulfotep, tebupirimfos, temephos, terbufos, tetrachlorvinphos,thiometon, triazophos, trichlorfon, vamidothion;

M.2. Carbamate compounds: aldicarb, alanycarb, bendiocarb, benfuracarb,butocarboxim, butoxycarboxim, carbaryl, carbofuran, carbosulfan,ethiofencarb, fenobucarb, formetanate, furathiocarb, isoprocarb,methiocarb, methomyl, metolcarb, oxamyl, pirimicarb, propoxur,thiodicarb, thiofanox, trimethacarb, XMC, xylylcarb, triazamate;

M.3. Pyrethroid compounds: acrinathrin, allethrin, d-cis-transallethrin, d-trans allethrin, bifenthrin, bioallethrin, bioallethrinS-cylclopentenyl, bioresmethrin, cycloprothrin, cyfluthrin,beta-cyfluthrin, cyhalothrin, lambda-cyhalothrin, gamma-cyhalothrin,cypermethrin, alpha-cypermethrin, beta-cypermethrin, theta-cypermethrin,zeta-cypermethrin, cyphenothrin, deltamethrin, empenthrin,esfenvalerate, etofenprox, fenpropathrin, fenvalerate, flucythrinate,flumethrin, tau-fluvalinate, halfenprox, imiprothrin, metofluthrin,permethrin, phenothrin, prallethrin, profluthrin, pyrethrin (pyrethrum),resmethrin, silafluofen, tefluthrin, tetramethrin, tralomethrin,transfluthrin;

M.4. Juvenile hormone mimics: hydroprene, kinoprene, methoprene,fenoxycarb, pyriproxyfen;

M.5. Nicotinic receptor agonists/antagonists compounds: acetamiprid,bensultap, cartap hydrochloride, clothianidin, dinotefuran,imidacloprid, thiamethoxam, nitenpyram, nicotine, spinosad (allostericagonist), spinetoram (allosteric agonist), thiacloprid, thiocyclam,thiosultap-sodium and AKD1022.

M.6. GABA gated chloride channel antagonist compounds: chlordane,endosulfan, gamma-HCH (lindane); ethiprole, fipronil, pyrafluprole,pyriprole

M.7. Chloride channel activators: abamectin, emamectin benzoate,milbemectin, lepimectin;

M.8. METI I compounds: fenazaquin, fenpyroximate, pyrimidifen,pyridaben, tebufenpyrad, tolfenpyrad, flufenerim, rotenone;

M.9. METI II and III compounds: acequinocyl, fluacyprim, hydramethylnon;

M.10. Uncouplers of oxidative phosphorylation: chlorfenapyr, DNOC;

M.11. Inhibitors of oxidative phosphorylation: azocyclotin, cyhexatin,diafenthiuron, fenbutatin oxide, propargite, tetradifon;

M.12. Moulting disruptors: cyromazine, chromafenozide, halofenozide,methoxyfenozide, tebufenozide;

M.13. Synergists: piperonyl butoxide, tribufos;

M.14. Sodium channel blocker compounds: indoxacarb, metaflumizone;

M.15. Fumigants: methyl bromide, chloropicrin sulfuryl fluoride;

M.16. Selective feeding blockers: crylotie, pymetrozine, flonicamid;

M.17. Mite growth inhibitors: clofentezine, hexythiazox, etoxazole;

M.18. Chitin synthesis inhibitors: buprofezin, bistrifluoron,chlorfluazuron, diflubenzuron, flucycloxuron, flufenoxuron,hexaflumuron, lufenuron, novaluron, noviflumuron, teflubenzuron,triflumuron;

M.19. Lipid biosynthesis inhibitors: spirodiclofen, spiromesifen,spirotetramat;

M.20. Octapaminergic agonsits: amitraz;

M.21. Ryanodine receptor modulators: flubendiamide and the phtalamidcompound (R)-,(S)-3-Chlor-N-1-{2-methyl-4-[1,2,2,2-tetrafluor-1-(trifluormethyl)ethyl]phenyl}-N2-(1-methyl-2-methylsulfonylethyl)phthalamid(M21.1)

M.22. Isoxazoline compounds:4-[5-(3,5-Dichloro-phenyl)-5-trifluoromethyl-4,5-dihydro-isoxazol-3-yl]-2-methyl-N-pyridin-2-ylmethyl-benzamide(M22.1),4-[5-(3,5-Dichloro-phenyl)-5-trifluoromethyl-4,5-dihydro-isoxazol-3-yl]-2-methyl-N-(2,2,2-trifluoro-ethyl)-benzamide(M22.2),4-[5-(3,5-Dichloro-phenyl)-5-trifluoromethyl-4,5-dihydro-isoxazol-3-yl]-2-methyl-N-[(2,2,2-trifluoro-ethylcarbannoyl)-methyl]-benzamide(M22.3),4-[5-(3,5-Dichloro-phenyl)-5-trifluoromethyl-4,5-dihydro-isoxazol-3-yl]-naphthalene-1-carboxylicacid [(2,2,2-trifluoro-ethylcarbamoyl)-methyl]amide (M22.4) and4-[5-(3,5-Dichlorophenyl)-5-trifluoromethyl-4,5-dihydro-isoxazol-3-yl]-N-[(methoxyimino)methyl]-2-methylbenzamide(M22.5);

M.23. Anthranilamide compounds: chloranthraniliprole, cyantraniliprole,5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid[4-cyano-2-(1-cyclopropyl-ethylcarbamoyl)-6-methyl-phenyl]-amide(M23.1), 5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid[2-chloro-4-cyano-6-(1-cyclopropylethylcarbamoyl)-phenyl]-amide (M23.2),5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid[2-bromo-4-cyano-6-(1-cyclopropyl-ethylcarbamoyl)-phenyl]-amide (M23.3),5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid[2-bromo-4-chloro-6-(1-cyclopropyl-ethylcarbamoyl)-phenyl]-amide(M23.4), 5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid[2,4-dichloro-6-(1-cyclopropyl-ethylcarbamoyl)-phenyl]-amide (M23.5),5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carboxylic acid[4-chloro-2-(1-cyclopropyl-ethylcarbamoyl)-6-methyl-phenyl]-amide(M23.6),N′-(2-{[5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carbonyl]-amino}-5-chloro-3-methyl-benzoyl)-hydrazinecarboxylicacid methyl ester (M23.7),N′-(2-{[5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carbonyl]-amino}-5-chloro-3-methyl-benzoyl)-N′-methyl-hydrazinecarboxylicacid methyl ester (M23.8),N′-(2-{[5-Bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carbonyl]-amino}-5-chloro-3-methyl-benzoyl)-N,N′-dimethyl-hydrazinecarboxylicacid methyl ester (M23.9),N′-(3,5-Dibromo-2-{[5-bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carbonyl]-amino}-benzoyl)-hydrazinecarboxylicacid methyl ester (M23.10),N′-(3,5-Dibromo-2-{[5-bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carbonyl]-amino}-benzoyl)-N′-methyl-hydrazinecarboxylicacid methyl ester (M23.11) andN′-(3,5-Dibromo-2-{[5-bromo-2-(3-chloro-pyridin-2-yl)-2H-pyrazole-3-carbonyl]-amino}-benzoyl)-N,N′-dimethyl-hydrazinecarboxylicacid methyl ester (M23.12);

M.24. Malononitrile compounds:2-(2,2,3,3,4,4,5,5-octafluoropentyl)-2-(3,3,3-trifluoropropyl)malononitrile(CF₂H—CF₂—CF₂—CF₂—CH₂—C(CN)₂—CH₂—CH₂—CF₃) (M24.1) and2-(2,2,3,3,4,4,5,5-octafluoropentyl)-2-(3,3,4,4,4-pentafluorobutyl)-malonodinitrile(CF₂H—CF₂—CF₂—CF₂—CH₂—C(CN)₂—CH₂—CH₂—CF₂—CF₃) (M24.2);

M.25. Microbial disruptors: Bacillus thuringiensis subsp. lsraelensi,Bacillus sphaericus, Bacillus thuringiensis subsp. Aizawai, Bacillusthuringiensis subsp. Kurstaki, Bacillus thuringiensis subsp.Tenebrionis;

M.26. Aminofuranone compounds:

-   4-{[(6-Bromopyrid-3-yl)methyl](2-fluoroethyl)amino}furan-2(5H)-on    (M26.1),-   4-{[(6-Fluoropyrid-3-yl)methyl](2,2-difluoroethyl)amino}furan-2(5H)-on    (M26.2),-   4-{[(2-Chloro1,3-thiazolo-5-yl)methyl](2-fluoroethyl)amino}furan-2(5H)-on    (M26.3),-   4-{[(6-Chloropyrid-3-yl)methyl](2-fluoroethyl)amino}furan-2(5H)-on    (M26.4),-   4-{[(6-Chloropyrid-3-yl)methyl](2,2-difluoroethyl)amino}furan-2(5H)-on    (M26.5),-   4-{[(6-Chloro-5-fluoropyrid-3-yl)methyl](methyl)amino}furan-2(5H)-on    (M26.6),-   4-{[(5,6-Dichloropyrid-3-yl)methyl](2-fluoroethyl)amino}furan-2(5H)-on    (M26.7),-   4-{[(6-Chloro-5-fluoropyrid-3-yl)methyl](cyclopropyl)amino}furan-2(5H)-on    (M26.8),-   4-{[(6-Chloropyrid-3-yl)methyl](cyclopropyl)amino}furan-2(5H)-on    (M26.9) and-   4-{[(6-Chloropyrid-3-yl)methyl](methyl)amino}furan-2(5H)-on    (M26.10);

M.27. Various compounds: aluminium phosphide, amidoflumet, benclothiaz,benzoximate, bifenazate, borax, bromopropylate, cyanide, cyenopyrafen,cyflumetofen, chinomethionate, dicofol, fluoroacetate, phosphine,pyridalyl, pyrifluquinazon, sulfur, organic sulfur compounds, tartaremetic, sulfoxaflor,N—R′-2,2-dihalo-1-R″cyclopropanecarboxamide-2-(2,6-dichloro-α,α,α-trifluoro-p-tolyl)hydrazoneorN—R″-2,2-di(R″′)propionamide-2-(2,6-dichloro-α,α,α-trifluoro-p-tolyl)-hydrazone,wherein R′ is methyl or ethyl, halo is chloro or bromo, R″ is hydrogenor methyl and R′″ is methyl or ethyl,4-But-2-ynyloxy-6-(3,5-dimethyl-piperidin-1-yl)-2-fluoro-pyrimidine(M27.1), Cyclopropaneacetic acid,1,1′-[(3S,4R,4aR,6S,6aS,12R,12aS,12bS)-4-[[(2-cyclopropylacetyl)oxy]methyl]-1,3,4,4a,5,6,6a,12,12a,12b-decahydro-12-hydroxy-4,6a,12b-trimethyl-11-oxo-9-(3-pyridinyl)-2H,11H-naphtho[2,1-b]pyrano[3,4-e]pyran-3,6-diyl]ester(M27.2) and8-(2-Cyclopropylmethoxy-4-trifluoromethyl-phenoxy)-3-(6-trifluoromethyl-pyridazin-3-yl)-3-aza-bicyclo[3.2.1]octane(M27.3).

The commercially available compounds of the group M may be found in ThePesticide Manual, 14th Edition, British Crop Protection Council (2006)among other publications.

Lepimectin is known from Agro Project, PJB Publications Ltd, November2004. Benclothiaz and its preparation have been described inEP-A1454621. Methidathion and Paraoxon and their preparation have beendescribed in Farm Chemicals Handbook, Volume 88, Meister PublishingCompany, 2001. Metaflumizone and its preparation have been described inEP-A1462 456. Flupyrazofos has been described in Pesticide Science 54,1988, p. 237-243 and in U.S. Pat. No. 4,822,779. Pyrafluprole and itspreparation have been described in JP 2002193709 and in WO 01/00614.Pyriprole and its preparation have been described in WO 98/45274 and inU.S. Pat. No. 6,335,357. Amidoflumet and its preparation have beendescribed in U.S. Pat. No. 6,221,890 and in JP 21010907. Flufenerim andits preparation have been described in WO 03/007717 and in WO 03/007718.AKD 1022 and its preparation have been described in U.S. Pat. No.6,300,348. Chloranthraniliprole has been described in WO 01/70671, WO03/015519 and WO 05/118552. Cyantraniliprole has been described in WO01/70671, WO 04/067528 and WO 05/118552. The anthranilamides M23.1 toM23.6 have been described in WO 2008/72743 and WO 200872783, those M23.7to M23.12 in WO2007/043677. The phthalamide M 21.1 is known from WO2007/101540. Cyflumetofen and its preparation have been described in WO04/080180. The aminoquinazolinone compound pyrifluquinazon has beendescribed in EP A 109 7932. Sulfoximine sulfoxaflor has been describedin WO 2006/060029 and WO 2007/149134. The alkynylether compound M27.1 isdescribed e.g. in JP 2006131529. Organic sulfur compounds have beendescribed in WO 2007060839. The isoxazoline compounds M 22.1 to M 22.5have been described in e.g. WO2005/085216, WO 2007/079162 and WO2007/026965. The aminofuranone compounds M 26.1 to M 26.10 have beendescribed eg. in WO 2007/115644. The pyripyropene derivative M 27.2 hasbeen described in WO 2008/66153 and WO 2008/108491. The pyridazincompound M 27.3 has been described in JP 2008/115155. Malononitrilecompounds as those (M24.1) and (M24.2) have been described in WO02/089579, WO 02/090320, WO 02/090321, WO 04/006677, WO 05/068423, WO05/068432 and WO 05/063694.

Fungicidal mixing partners are in particular those selected from thegroup consisting of acylalanines such as benalaxyl, metalaxyl, ofurace,oxadixyl,

amine derivatives such as aldimorph, dodine, dodemorph, fenpropimorph,fenpropidin, guazatine, iminoctadine, spiroxamin, tridemorph,

anilinopyrimidines such as pyrimethanil, mepanipyrim or cyrodinyl,

antibiotics such as cycloheximid, griseofulvin, kasugamycin, natamycin,polyoxin or streptomycin,

azoles such as bitertanol, bromoconazole, cyproconazole, difenoconazole,diniconazole, epoxiconazole, fenbuconazole, fluquiconazole, flusilazole,hexaconazole, imazalil, metconazole, myclobutanil, penconazole,propiconazole, prochloraz, prothioconazole, tebuconazole, triadimefon,triadimenol, triflumizol, triticonazole, flutriafol, dicarboximides suchas iprodion, myclozolin, procymidon, vinclozolin,dithiocarbamates such as ferbam, nabam, maneb, mancozeb, metam, metiram,propineb, polycarbamate, thiram, ziram, zineb,heterocyclic compounds such as anilazine, benomyl, boscalid,carbendazim, carboxin, oxycarboxin, cyazofamid, dazomet, dithianon,famoxadon, fenamidon, fenarimol, fuberidazole, flutolanil, furametpyr,isoprothiolane, mepronil, nuarimol, probenazole, proquinazid, pyrifenox,pyroquilon, quinoxyfen, silthiofam, thiabendazole, thifluzamid,thiophanate-methyl, tiadinil, tricyclazole, triforine,copper fungicides such as Bordeaux mixture, copper acetate, copperoxychloride, basic copper sulfate,nitrophenyl derivatives such as binapacryl, dinocap, dinobuton,nitrophthalisopropyl, phenylpyrroles such as fenpiclonil or fludioxonil,sulfur,other fungicides such as acibenzolar-S-methyl, benthiavalicarb,carpropamid, chlorothalonil, cyflufenamid, cymoxanil, diclomezin,diclocymet, diethofencarb, edifenphos, ethaboxam, fenhexamid,fentin-acetate, fenoxanil, ferimzone, fluazinam, fosetyl,fosetyl-aluminum, iprovalicarb, hexachlorobenzene, metrafenon,pencycuron, propamocarb, phthalide, toloclofos-methyl, quintozene,zoxamid,strobilurins such as azoxystrobin, dimoxystrobin, enestroburin,fluoxastrobin, kresoxim-methyl, me-tominostrobin, orysastrobin,picoxystrobin, pyraclostrobin, pyribencarb or trifloxystrobin,sulfenic acid derivatives such as captafol, captan, dichlofluanid,folpet, tolylfluanid, cinnemamides and analogs such as dimethomorph,flumetover or flumorph.

The invertebrate pest, i.e. arthropodes and nematodes, the plant, soilor water in which the plant is growing can be contacted with thecompound(s) of formulae I or II or composition(s) containing them by anyapplication method known in the art. As such, “contacting” includes bothdirect contact (applying the compounds/compositions directly on theinvertebrate pest or plant—typically to the foliage, stem or roots ofthe plant) and indirect contact (applying the compounds/compositions tothe locus of the invertebrate pest or plant).

Moreover, invertebrate pests may be controlled by contacting the targetpest, its food supply, habitat, breeding ground or its locus with apesticidally effective amount of compounds of formulae I or II. As suchthe application may be carried out before or after the infection of thelocus, growing crops, or harvested crops by the pest.

“Locus” in general means a habitat, breeding ground, cultivated plants,plant propagation material (such as seed), soil, area, material orenvironment in which a pest or parasite is growing or may grow.

In general “pesticidally effective amount” means the amount of activeingredient needed to achieve an observable effect on growth, includingthe effects of necrosis, death, retardation, prevention, and removal,destruction, or otherwise diminishing the occurrence and activity of thetarget organism. The pesticidally effective amount can vary for thevarious compounds/compositions used in the invention. A pesticidallyeffective amount of the compositions will also vary according to theprevailing conditions such as desired pesticidal effect and duration,weather, target species, locus, mode of application, and the like.

The compounds of formulae I or II and the compositions comprising saidcompounds can be used for protecting wooden materials such as trees,board fences, sleepers, etc. and buildings such as houses, outhouses,factories, but also construction materials, furniture, leathers, fibers,vinyl articles, electric wires and cables etc. from ants and/ortermites, and for controlling ants and termites from doing harm to cropsor human being (e.g. when the pests invade into houses and publicfacilities). The compounds of formula I and II are applied not only tothe surrounding soil surface or into the under-floor soil in order toprotect wooden materials but it can also be applied to lumbered articlessuch as surfaces of the under-floor concrete, alcove posts, beams,plywood, furniture, etc., wooden articles such as particle boards, halfboards, etc. and vinyl articles such as coated electric wires, vinylsheets, heat insulating material such as styrene foams, etc. In case ofapplication against ants doing harm to crops or human beings, the antcontroller of the present invention is applied to the crops or thesurrounding soil, or is directly applied to the nest of ants or thelike.

The compounds of formulae I and II can also be applied preventively toplaces at which occurrence of the pests is expected.

The compounds of formulae I or II may also be used to protect growingplants from attack or infestation by pests by contacting the plant witha pesticidally effective amount of compounds of formula I or II. Assuch, “contacting” includes both direct contact (applying thecompounds/compositions directly on the pest and/or plant—typically tothe foliage, stem or roots of the plant) and indirect contact (applyingthe compounds/compositions to the locus of the pest and/or plant).

In the case of soil treatment or of application to the pests dwellingplace or nest, the quantity of active ingredient ranges from 0.0001 to500 g per 100 m², preferably from 0.001 to 20 g per 100 m².

Customary application rates in the protection of materials are, forexample, from 0.01 g to 1000 g of active compound per m² treatedmaterial, desirably from 0.1 g to 50 g per m².

Insecticidal compositions for use in the impregnation of materialstypically contain from 0.001 to 95% by weight, preferably from 0.1 to45% by weight, and more preferably from 1 to 25% by weight of at leastone repellent and/or insecticide.

For use in bait compositions, the typical content of active ingredientis from 0.001 by weight to 15% by weight, desirably from 0.001% byweight to 5% by weight of active compound.

For use in spray compositions, the content of active ingredient is from0.001 to 80% by weight, preferably from 0.01 to 50% by weight and mostpreferably from 0.01 to 15% by weight.

For use in treating crop plants, the rate of application of the activeingredients of this invention may be in the range of 0.1 g to 4000 g perhectare, desirably from 5 g to 600 g per hectare, more desirably from 10g to 300 g per hectare.

In the treatment of seed, the application rates of the activeingredients are generally from 0.1 g to 10 kg per 100 kg of seed,preferably from 1 g to 1 kg per 100 kg of seed, in particular from 1 gto 250 g per 100 kg of seed, in particular from 50 g to 150 g per 100 kgof seed.

The present invention is now illustrated in further detail by thefollowing examples but is not limited to them.

I. PREPARATION EXAMPLES

The procedures described in the following preparation examples were usedto prepare further compounds of formulae (Ia) by appropriatemodification of the starting material. The resulting compounds, togetherwith physical data, are listed below.

Products were characterized by HPLC (High Performance LiquidChromatography Mass Spectrometry). HPLC was carried out using ananalytic RP-18 column (Chromolith Speed ROD from Merck KgaA, Germany)which was operated at 40° C. Acetonitrile with 0.1 by volume of atrifluoroacetic acid/water mixture and 0.1 by volume of trifluoroaceticacid served as mobile phase; flow rate: 1.8 ml/min and injection volume:2 μl.

Example 15 3-Cyclopropyl-isoxazole-4-carboxylic acid pyridin-3-ylamide3-Cyclopropyl-isoxazole-4-carboxylic acid

5.6 g (31 mmol) of 3-Cyclopropyl-isoxazole-4-carboxylic acid ethyl esterwere slowly added to a solution of 6.1 g (93 mmol, 85% purity) ofpotassium hydroxide in ethanol/water (1:3, 100 ml) at 0° C. The reactionmixture was stirred at room temperature for 16 h, diluted with water,acidified (pH=2) with 20% aqueous HCl and extracted withdichloromethane. The combined organic layers were dried over sodiumsulfate, filtered and the solvent was removed to yield 4.7 g (94%, 95%purity) of the title compound which did not need further purification.

3-Cyclopropyl-isoxazole-4-carboxylic acid pyridin-3-ylamide

400 mg (2.6 mmol) of 3-cyclopropyl-isoxazole-4-carboxylic acid weresuspended in 10 mL of toluene and one drop of dimethylformamide wasadded to the mixture. 0.24 mL of thionylchloride (3.3 mmol) were addedat room temperature and the reaction mixture was stirred at 65° C. fortwo hours. After removal of the solvent, toluene was added and theevaporation was repeated. The obtained residue was then dissolved in 5mL of dichloromethane and the solution was added dropwise to a solutioncontaining 246 mg pyridin-3-ylamine (2.6 mmol) and 0.45 ml triethylamine (3.3 mmol) in 5 ml dichloromethane. The mixture was stirred atroom temperature for 16 h and the solvent was removed under vacuum. Theresidue was purified by flash column chromatography (silica, gradientelution cyclohexane→ethyl acetate→methanol) and the solvent was removedunder vacuum to give 436 mg (69%, 95% purity) of the title compound as abrown solid.

Example 2 5-Br-thiazole-4-carboxylic acid pyridin-3-yl-amide

150 mg (0.43 mmol) of 5-bromo-thiazole-4-carboxylic acid and 81.4 mg(0.87 mmol) of pyridin-3-yl-amine were dissolved in 6 ml dimethylformamide. 0.09 mL (0.65 mmol) of triethyl amine followed by 225 mg(0.43 mmol) of 1H-benzotriazol-1-yloxytri-pyrrolidinophosphoniumhexafluorophosphate (PyBOP) were added and the reaction mixture wasstirred at room temperature for 16 h. Brine was added and the reactionmixture was extracted two times with dichloromethane. The combinedorganic layers were dried over sodium sulfate, filtered and the solventwas removed under reduced pressure. The obtained residue was purified byflash column chromatography (silica, gradient elution cyclohexane→ethylacetate→methanol) to give 90 mg (66%, 90% purity) of the title compound.

Compounds of formula (Ia) prepared according to the above mentionedmethod together with their physico-chemical data are compiled below. R¹and A in each case have the meanings given in the corresponding line andR² and R³ in each case are hydrogen. The corresponding physico-chemicaldata r.t. ═HPLC retention time is given.

physico- chemical data: Example R¹ A r.t. [min] 1 H 5-Br-thiazol-4-yl1.494 2 Me 2-(4-Cl-phenyl)-oxazol-4-yl 2.414 3 Me 3-Me-isoxazol-4-yl1.115 4 H 3-Me-isoxazol-4-yl 1.272 5 H 4-Me-thiazol-5-yl 1.199 6 Me3-Et-isoxazol-4-yl 1.434 7 Me 4-Me-thiazol-5-yl 1.123 8 H3-Et-isoxazol-4-yl 1.562 9 H 3-Cyclopropyl-isoxazol-4-yl 1.612 10 Me3-Cyclopropyl-isoxazol-4-yl 1.490 11 H 3-Methyl-5-phenyl-isoxazol-4-yl2.034 12 H 1H-Imidazol-2-yl 0.610 13 H 1H-Imidazol-4-yl 0.563 14 H2-Methyl-1H-imidazol-4-yl 0.548 15 H 3-Cyclopropyl-isoxazol-5-yl 1.61116 H 2-Methyl-5-(trifluoromethyl)-oxazol-4-yl 1.806 17 H2-Methyl-4-(trifluormethyl)-thiazol-5-yl 1.643 18 H5-Methyl-2-(4-trifluoromethylphenyl)-3H- 2.323 imidazol-4-yl 19 H2,5-Dimethyl-oxazol-4-yl 1.496 20 H 5-Methyl-oxazol-4-yl 1.288 21 H4-Methyl-oxazol-5-yl 1.035 22 H Oxazol-5-yl 0.886 23 H2,4-Dimethyl-oxazol-5-yl 1.255 24 H 2,4-Dimethyl-thiazol-5-yl 1.348 25 H2-Methyl-oxazol-4-yl 1.577 26 H Isothiazol-5-yl 1.166

II. EVALUATION OF PESTICIDAL ACTIVITY

II.1 Cotton Aphid (Aphis gossypii, Mixed Life Stages)

Method a)

The active compounds were formulated in 50:50 (vol:vol) acetone: waterand 100 ppm Kinetica™ (from Helena Chemical Co.) surfactant.

Cotton plants at the cotyledon stage (one plant per pot) were infestedby placing a heavily infested leaf from the main colony on top of eachcotyledon. The aphids were allowed to transfer to the host plantovernight, and the leaf used to transfer the aphids was removed. Thecotyledons were dipped in the test solution and allowed to dry. After 5days, mortality counts were made.

In this test, the compounds 4, 5, 15, 17, 19, 20, 21, 22, 23, 24 and 25respectively, at 300 ppm showed a mortality of at least 90% incomparison with untreated controls.

Method b)

The active compounds were formulated in cyclohexanone as a 10,000 ppmsolution supplied in 1.3 ml ABgene® (from ABgene) tubes. These tubeswere inserted into an automated electrostatic sprayer equipped with anatomizing nozzle and they served as stock solutions for which lowerdilutions were made in 50% acetone:50% water (v/v). A nonionicsurfactant (Kinetic® from Helena Chemical Co.) was included in thesolution at a volume of 0.01% (v/v).

Cotton plants at the cotyledon stage were infested with aphids prior totreatment by placing a heavily infested leaf from the main aphid colonyon top of each cotyledon. Aphids were allowed to transfer overnight toaccomplish an infestation of 80-100 aphids per plant and the host leafwas removed. The infested plants were then sprayed by an automatedelectrostatic plant sprayer equipped with an atomizing spray nozzle. Theplants were dried in the sprayer fume hood, removed from the sprayer,and then maintained in a growth room under fluorescent lighting in a24-hr photoperiod at 25° C. and 20-40% relative humidity. Aphidmortality on the treated plants, relative to mortality on untreatedcontrol plants, was determined after 5 days.

In this test, the compounds 3, 5, 6, 7, 8, 9, 10 and 11 respectively, at300 ppm showed a mortality of at least 75% in comparison with untreatedcontrols.

II.2 Green Peach Aphid (Myzus persicae, Mixed Life Stages)

Method a)

The active compounds were formulated in 50:50 (vol:vol) acetone:waterand 100 ppm Kinetica™ (from Helena Chemical Co.) surfactant.

Pepper plants in the 2^(nd) leaf-pair stage (variety ‘CaliforniaWonder’) were infested with approximately 40 laboratory-reared aphids byplacing infested leaf sections on top of the test plants. The leafsections were removed after 24 hr. The leaves of the intact plants weredipped into gradient solutions of the test compound and allowed to dry.Test plants were maintained under fluorescent light (24 hourphotoperiod) at about 25° C. and 20-40% relative humidity. Aphidmortality on the treated plants, relative to mortality on check plants,was determined after 5 days.

In this test, compounds 4, 5, 15, 16, 17, 21, 22, 23, 24 and 25respectively, at 300 ppm showed a mortality of at least 90% incomparison with untreated controls.

Method b)

The active compounds were formulated in cyclohexanone as a 10,000 ppmsolution supplied in 1.3 ml ABgene® (from ABgene) tubes. These tubeswere inserted into an automated electrostatic sprayer equipped with anatomizing nozzle and they served as stock solutions for which lowerdilutions were made in 50 acetone:50% water (v/v). A nonionic surfactant(Kinetic®) (from Helena Chemical Co.) was included in the solution at avolume of 0.01% (v/v).

Bell pepper plants at the first true-leaf stage were infested prior totreatment by placing heavily infested leaves from the main colony on topof the treatment plants. Aphids were allowed to transfer overnight toaccomplish an infestation of 30-50 aphids per plant and the host leaveswere removed. The infested plants were then sprayed by an automatedelectrostatic plant sprayer equipped with an atomizing spray nozzle. Theplants were dried in the sprayer fume hood, removed, and then maintainedin a growth room under fluorescent lighting in a 24-hr photoperiod at25° C. and 20-40% relative humidity. Aphid mortality on the treatedplants, relative to mortality on untreated control plants, wasdetermined after 5 days.

In this test, the compounds 2, 3, 5, 6, 8, 9 and 10 respectively, at 300ppm showed a mortality of at least 75% in comparison with untreatedcontrols.

II.3 Cowpea Aphid (Aphis craccivora)

The active compounds were formulated in 50:50 (vol:vol) acetone:water.The test solution was prepared at the day of use.

Potted cowpea plants colonized with 100-150 aphids of various stageswere sprayed after the pest population had been recorded. Populationreduction was assessed after 24, 72, and 120 hours.

In this test, the compounds 3, 4, 5, 6, 8, 9, 10, 12, 13, 14, 15, 19,20, 21, 22, 23, 24, 25 and 26 respectively, at 300 ppm showed amortality of at least 90% in comparison with untreated controls.

II.4 Vetch Aphid (Megoura viciae)

The active compounds were formulated in 1:3 (vol:vol) DMSO:water withdifferent concentrations of formulated compounds.

Bean leaf disks were placed into microtiterplates filled with 0.8agar-agar and 2.5 ppm OPUS™ (from BASF SE, conazole). The leaf diskswere sprayed with 2.5 μl of the test solution and 5 to 8 adult aphidswere placed into the microtiterplates which were then closed and kept at23±1° C. and 50±5% relative humidity under fluorescent light for 6 days.Mortality was assessed on the basis of vital, reproduced aphids. Aphidmortality and fecundity was then visually assessed.

In this test, the compounds 4, 5, 9, 10, 13, 15, 17, 19, 20, 21, 23 and24 respectively at a concentration of the test solution of 2500 mg/Lshowed a mortality of at least 90%.

II.5 Boll Weevil (Anthonomus grandis)

The compounds were formulated in 75:25 (vol:vol) water:DMSO.

For evaluating control of boll weevil (Anthonormus grandis) the testunit consisted of 24-well-microtiter plates containing an insect dietand 20-30 A. grandis eggs. Different concentrations of formulatedcompounds were sprayed onto the insect diet at 20 μl, using a custombuilt micro atomizer, at two replications. After application, themicrotiter plates were incubated at 23±1° C. and 50±5% relative humidityfor 5 days. Egg and larval mortality was then visually assessed.

In this test, the compounds 4, 5, 10, 14, 18 and 23 respectively at aconcentration of the test solution of 2500 mg/L showed a mortality of atleast 50%.

II.6 Activity Against Green Peach Aphid (Myzus persicae)

For evaluating control of green peach aphid (Myzus persicae) throughsystemic means the test unit consisted of 96-well-microtiter platescontaining liquid artificial diet under an artificial membrane.

The compounds were formulated using a solution containing 75% v/v waterand 25% v/v DMSO. Different concentrations of formulated compounds werepipetted into the aphid diet, using a custom built pipetter, at tworeplications. After application, 5 to 8 adult aphids were placed on theartificial membrane inside the microtiter plate wells. The aphids werethen allowed to suck on the treated aphid diet and incubated at about23+1° C. and about 50+5% relative humidity for 3 days. Aphid mortalityand fecundity was then visually assessed.

In this test, compounds 4, 5, 9, 10, 15, 17, 20, 22, 23, 24 and 25respectively, at 2500 ppm showed 100% mortality in comparison withuntreated controls.

II.7 Activity Against Brown Planthopper (Nilaparvata lugens)

The active compounds were formulated as a 50:50 (vol:vol) acetone:watersolution. Surfactant (Alkamuls EL 620) (Rhone-Poulenc) was added at therate of 0.1% (vol/vol). Rice seedlings were cleaned and washed 24 hbefore spraying. Potted rice seedlings were sprayed with 5 ml testsolution, air dried, placed in cages and inoculated with 10 adults.Treated rice plants were kept at 28-29° C. and relative humidity of50-60% mortality was recorded after 72 hours.

In this test, compounds 1, 4 and 20 respectively at 500 ppm showed amortality of at least 50% in comparison with untreated controls.

II.8 Activity in the Hydroponic Tests Against Green Peach Aphids (Myzuspersicae)

Green pepper plants (Capsicum annuum L., variety ‘California Wonder’)are grown in the greenhouse from seed to the second true leaf stage(BBCH 12) in Scott's MetroMix® 360 (Sungro Horticulture) (1-2 plants per2¼″ square pot). Cotyledon leaves are removed and roots are rinsed intap water until free of soil. The roots are kept moist under a layer ofwet paper toweling until all plants have been prepared.

A 3400 ppm stock solution is prepared of each test compound usingreagent grade acetone as the solvent. Subsequent dilutions of 100 and 10ppm are prepared from this stock with final dilutions in deionized waterin 100 ml amber glass bottles. One bare root plant is placed in eachbottle using a foam plug section to centrally secure the stem in thebottleneck. The bare roots are fully-immersed in the test suspensions.Host plants are placed in a plant growth room under continuous GroLux®fluorescent lighting (40 W), for 24 hours at 25±2° C. and 20-40% RH.

After exposure of the bare roots to the test suspensions, pieces ofpepper plants infested with green peach aphid (Myzus persicae) areplaced on top of the test foliage. Insects are allowed to transfer fromthe host leaves to accomplish an infestation of 40-50 insects per plant.The assay is allowed to run for 3 days in the same growth chamber asused previously. Assessments include estimates of aphid populationdensity reduction relative to the average density of aphids on theuntreated control plants. Phytotoxic responses of the host plants arealso recorded at this time.

In this test, compounds 3, 4, 8 and 10 respectively at 100 ppm showed amortality of at, least 75% in comparison with untreated controls.

II.9 Activity in the Hydroponic Tests Against Cotton Aphids (Aphisgossypii)

Cotton plants (Gossypium hirsutum, variety ‘Sure Grow 747’) are grown inthe greenhouse from seed to the second true leaf stage (BBCH 12) inScott's Metro-Mix® 360 (Sungro Horticulture) (1-2 plants per 2¼″ squarepot). Cotyledon leaves are removed and roots are rinsed in tap wateruntil free of soil. The roots are kept moist under a layer of wet papertoweling until all plants have been prepared.

A 3400 ppm stock solution is prepared of each test compound usingreagent grade acetone as the solvent. Subsequent dilutions of 100 and 10ppm are prepared from this stock with final dilutions in deionized waterin 100 ml amber glass bottles. One bare root plant is placed in eachbottle using a foam plug section to centrally secure the stem in thebottleneck. The bare roots are fully-immersed in the test suspensions.Host plants are placed in a plant growth room under continuous GroLux®fluorescent lighting (40 W), for 24 hours at 25+2° C. and 20-40% RH.

After exposure of the bare roots to the test suspensions, pieces ofcotton plants infested with cotton aphids (Aphis gossypii) are placed ontop of the test foliage. Insects are allowed to transfer from the hostleaves to accomplish an infestation of 40-50 insects per plant. Theassay is allowed to run for 3 days in the same growth chamber as usedpreviously. Assessments include estimates of aphid population densityreduction relative to the average density of aphids on the untreatedcontrol plants. Phytotoxic responses of the host plants are alsorecorded at this time.

In this test, compounds 3, 6, 8, 9 and 10 respectively at 100 ppm showeda mortality of at least 75% in comparison with untreated controls.

The invention claimed is:
 1. A method for controlling and/or combatinginsects which method comprises treating the insects, their food supply,their habitat or their breeding ground or a plant, seed, soil, area,material or environment in which the insects are growing or may grow, orthe materials, plants, seeds, soils, surfaces or spaces to be protectedfrom insect attack or infestation with a pesticidal effective amount ofa compound of formula (I), or a salt or an N-oxide thereof:

wherein A is an isoxazole or isothiazole radical of formula A1a, A2a, orA3a

# denotes the bonding site to the remainder of formula (I) X³ is a lonepair or oxygen; Z is O or S; R¹ is hydrogen, C₁-C₃-alkyl orC₁-C₄-alkylene-CN; R² is hydrogen, methyl, difluoromethyl,trifluoromethyl, methoxy, difluoromethoxy or trifluoromethoxy; R³ ishydrogen, methyl, difluoromethyl, trifluoromethyl, methoxy,difluoromethoxy or trifluoromethoxy; R^(41a), R^(43a), R^(52a), andR^(53a) are independently selected from the group consisting ofhydrogen, halogen, CN, NO₂, C₁-C₁₀-alkyl, C₃-C₁₀-cycloalkyl,C₅-C₁₀-cycloalkenyl, C₃-C₁₀-cycloalkylmethyl, C₂-C₁₀-alkenyl,C₂-C₁₀-alkynyl, wherein the aliphatic or cyclic moieties in the 6 lastmentioned radicals may be unsubstituted, may be partially or fullyhalogenated, or may carry 1 or 2 identical or different substituentsR^(y) wherein R^(y) is selected from halogen, cyano, nitro, C₁-C₄-alkyl,C₁-C₄-haloalkyl, C₁-C₄-alkoxy, C₁-C₄-haloalkoxy, S(O)_(m)R^(d),S(O)_(m)NR^(e)R^(f), C₁-C₄-alkylcarbonyl, C₁-C₄-haloalkylcarbonyl,C₁-C₄-alkoxycarbonyl, C₁-C₄-haloalkoxycarbonyl, C₃-C₆-cycloalkyl,C₃-C₆-halocycloalkyl, C₂-C₄-alkenyl, C₂-C₄-haloalkenyl, C₂-C₄-alkynyland C₁-C₄-alkoxy-C₁-C₄-alkyl wherein m is 0, 1 or 2 and R^(d)C₁-C₄-alkylor C₁-C₄-haloalkyl; with the proviso that either R^(41a) or R^(51a) is Hif Z is O; R^(42a) is selected from the group consisting of hydrogen,halogen, NO₂, C₁-C₁₀-alkyl, C₃-C₁₀-cycloalkyl, C₅-C₁₀-cycloalkenyl,C₃-C₁₀-cycloalkylmethyl, C₂-C₁₀-alkenyl, C₂-C₁₀-alkynyl, wherein thealiphatic or cyclic moieties in the 6 last mentioned radicals may beunsubstituted, may be partially or fully halogenated; X¹ is O.
 2. Themethod as claimed in claim 1, wherein the pesticidal compound is acompound of the formula (I), wherein R¹ is hydrogen, methyl or ethyl. 3.The method as claimed in claim 1, wherein in formula (I) A is a radicalA1a, R^(41a) and R^(51a) are independently selected from the groupconsisting of hydrogen, halogen, C₁-C₁₀-alkyl, C₃-C₁₀-cycloalkyl,C₂-C₁₀-alkenyl and C₂-C₁₀-alkynyl, wherein the aliphatic or cyclicmoieties in the 4 last mentioned radicals may be unsubstituted, may bepartially or fully halogenated or may carry 1 or 2 identical ordifferent substituents R^(y) wherein R^(y) is selected from halogen,cyano, nitro, C₁-C₄-alkyl, C₁-C₄-haloalkyl, C₁-C₄-alkoxy,C₁-C₄-haloalkoxy, S(O)_(m)R^(d), S(O)_(m)NR^(e)R^(f),C₁-C₄-alkylcarbonyl, C₁-C₄-haloalkylcarbonyl, C₁-C₄-alkoxycarbonyl,C₁-C₄-haloalkoxycarbonyl, C₃-C₆-cycloalkyl, C₃-C₆-halocycloalkyl,C₂-C₄-alkenyl, C₂-C₄-haloalkenyl, C₂-C₄-alkynyl andC₁-C₄-alkoxy-C₁-C₄-alkyl wherein m is 0, 1 or 2 and R^(d)C₁-C₄-alkyl orC₁-C₄-haloalkyl.
 4. The method as claimed in claim 1, wherein theinsects are of the order Homoptera.